US8779126B2 - Dye, photoelectric conversion element using the same, photoelectrochemical cell, and method of producing dye - Google Patents

Dye, photoelectric conversion element using the same, photoelectrochemical cell, and method of producing dye Download PDF

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US8779126B2
US8779126B2 US13/126,951 US200913126951A US8779126B2 US 8779126 B2 US8779126 B2 US 8779126B2 US 200913126951 A US200913126951 A US 200913126951A US 8779126 B2 US8779126 B2 US 8779126B2
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dye
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US20110213144A1 (en
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Katsumi Kobayashi
Keizo Kimura
Tatsuya Susuki
Hirotaka Satou
Yukio Tani
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0091—Methine or polymethine dyes, e.g. cyanine dyes having only one heterocyclic ring at one end of the methine chain, e.g. hemicyamines, hemioxonol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • H01M14/005—Photoelectrochemical storage cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/652—Cyanine dyes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a dye, a photoelectric conversion element sensitized with a dye, and a photoelectrochemical cell (dye-sensitized solar cell) using the same. Further, the present invention relates to a method of producing a dye.
  • Photoelectric conversion elements are used in various photosensors, copying machines, solar cells, and the like. These photoelectric conversion elements have adopted various systems to be put into use, such as elements utilizing metals, elements utilizing semiconductors, elements utilizing organic pigments or dyes, or combinations of these elements. Among them, solar cells that make use of non-exhaustive solar energy do not necessitate fuels, and full-fledged practicalization of solar cells as an inexhaustible clean energy is being highly expected. Under such circumstances, research and development of silicon-based solar cells have long been in progress. Many countries also support policy-wise considerations, and thus dissemination of silicon-based solar cells is still in progress. However, silicon is an inorganic material, and has limitations per se in terms of throughput and molecular modification.
  • Patent Literatures 1 to 3 describe dye-sensitized photoelectric conversion elements making use of semiconductor fine particles sensitized by a dye, to which the foregoing technology has been applied. These have an advantageous that a device can be produced by relatively simple steps.
  • the ruthenium complex dyes used in the sensitized dyes are very expensive.
  • there are concerns about the supply of ruthenium and it still cannot be said that this technology is satisfactory as a next-generation technology supporting clean energy to cope with the above-described problems in a full-fledged manner. Rather, the research and development intended for practicalization has been just begun to some extent.
  • the problem of the present invention is to provide a photoelectrochemical cell having high conversion efficiency using a low-cost dye.
  • the dye of the first embodiment of the present invention is a specific dye having a cyclic structure containing a carbon atom and a nitrogen atom, in which an acidic group binds to the nitrogen atom of the cyclic structure through a single bond or a divalent linking group, and the exomethylene of the cyclic structure is substituted with one or more acidic group(s).
  • a dye having a structure represented by formula (1A):
  • Y 1A and Y 2A represents an acidic group, in which when they each represent an acidic group, they may be the same as or different from each other, or when only one of them represents an acidic group, the other represents an electron-withdrawing group;
  • LL represents at least one divalent linking group selected from the group consisting of an alkenylene group, an alkynylene group and an arylene group, each of which may have a substituent;
  • Y 3A represents an acidic group;
  • R A , R 1A , R 2A and R 3A each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group linked through a carbon atom;
  • R 1A and R 2A may form a ring together with the substituent on LL; and
  • L has the same meaning as in formula (1A).
  • Y 1A and Y 2A represents an acidic group, in which when they each represent an acidic group, they may be the same as or different from each other, or when only one of them represents an acidic group, the other represents an electron-withdrawing group;
  • LL represents at least one divalent linking group selected from the group consisting of an alkenylene group, an alkynylene group and an arylene group, each of which may have a substituent;
  • Y 3A represents an acidic group;
  • R 3A and R 4A each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group linked through a carbon atom;
  • B represents a group of atoms necessary for forming a ring together with the two carbon atoms and the nitrogen atom on the benzene ring; and
  • L has the same meaning as in formula (1A).
  • Y 1A and Y 2A represents an acidic group, in which when they each represent an acidic group, they may be the same as or different from each other, or when only one of them represents an acidic group, the other represents an electron-withdrawing group;
  • LL represents at least one divalent linking group selected from the group consisting of an alkenylene group, an alkynylene group and an arylene group, each of which may have a substituent;
  • Y 3A represents an acidic group;
  • R A , R 3A and R 4A each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group linked through a carbon atom;
  • B represents a group of atoms necessary for forming a ring together with the two carbon atoms and the nitrogen atom on the benzene ring; and
  • L has the same meaning as in formula (1A).
  • ⁇ 5a> The dye described in any one of the items ⁇ 1a> to ⁇ 4a>, wherein the acidic group of Y 1A and Y 2A is a carboxyl group.
  • a method of producing a dye which comprises the step of:
  • A, D, n and L each have the same meanings as those in formula (1A), respectively; at lease one of Z 1A , Z 2A and Z 3A represents a substituent represented by formula (9A), and Z 1A , Z 2A and Z 3A each are not the substituent represented by formula (9A), each represent an acidic group, in which any one of Z 1A and Z 2A represents an electron-withdrawing group.
  • a photoelectric conversion element comprising a light-receiving electrode, wherein the light-receiving electrode comprises semiconductor fine particles sensitized by the dye described in any one of the items ⁇ 1 a> to ⁇ 5a>.
  • ⁇ 8a> A photoelectrochemical cell, comprising the photoelectric conversion element described in the above item ⁇ 7a>.
  • the dye of the second embodiment of the present invention is a dye having a specific structure containing benzene rings linked with a nitrogen-containing 7-membered heterocyclic ring.
  • a dye having a structure represented by formula (1B):
  • X represents a group of non-metallic atoms necessary for forming a nitrogen-containing 7-membered hetero ring by linking with the benzene rings;
  • Y represents a group to give a dye;
  • n represents an integer of 1 or more;
  • Z represents a substituent;
  • m represents zero (0) or a positive integer; when m is an integer of 2 or more, Z's may be the same as or different from each other; and
  • R 1B represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group that is linked with the nitrogen atom via a carbon atom.
  • X represents a group of non-metallic atoms necessary for forming a nitrogen-containing 7-membered hetero ring by linking with the benzene rings
  • R 1B represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group that is linked with the nitrogen atom via a carbon atom
  • R 2B to R 9B each independently represent a hydrogen atom or a substituent
  • at least one substituent of R 2B to R 9B represents a group to give a dye represented by formula (3B);
  • R 10B , R 11B and R 13B each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; r represents an integer of 0 or more; the carbon-carbon double bond in formula (3B) may be any of an E-form and a Z-form; and R 12B represents a group having at least one acidic group, or an acidic nucleus.
  • R 1B to R 3B and R 5B to R 13B in formula (4B) each have the same meaning as R 1B to R 3B and R 5B to R 13B in formula (2B) or (3B), respectively.
  • R 1B to R 13B in formula (5B) each have the same meaning as R 1 B to R 13B in formula (2B) or (3B), respectively; and R 14B represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group or a heterocyclic group.
  • R 1B to R 3B , R 5B , R 6B and R 8B to R 13B in formula (6B) each have the same meaning as R 1B to R 3B , R 5B , R 6B and R 8B to R 13B in formula (2B) or (3B), respectively.
  • R 15B and R 16B each independently represent an aliphatic group, an aromatic group, or a heterocyclic group (at least one functional group thereof may have an acidic group); 1 represents 0 or 1; the carbon-carbon double bonds in formula (7B) may be any of an E-form or a Z-form; R 17B in formula (7B) represents a sulfur atom or a group represented by formula (9B); and the carbon-carbon double bond in formula (9B) may be any of an E-form or a Z-form;
  • R 18B and R 19B each independently represent a cyano group or an acidic group, and may be the same as or different from each other; and the carbon-carbon double bond in formula (8B) may be any of an E-form or a Z-form;
  • R 20B and R 21B each independently represent a cyano group or an acidic group, and may be the same as or different from each other; and the carbon-carbon double bond in formula (9B) may be any of an E-form or a Z-form.
  • R 16B represents an aliphatic group, an aromatic group or a heterocyclic group (each of which may have an acidic group).
  • R 15B represents an aliphatic group, an aromatic group or a heterocyclic group (each of which may have an acidic group).
  • a photoelectric conversion element comprising a light-receiving electrode, wherein the light-receiving electrode comprises semiconductor fine particles sensitized by the dye described in any one of the items ⁇ 1b> to ⁇ 9b>.
  • the dye of the third embodiment of the present invention has a 6-membered or 7-membered nitrogen-containing heterocyclic ring linked with a benzene ring, and has a substituent having a specific structure on the benzene ring.
  • a 1 represents a 6- or 7-membered nitrogen-containing heterocycle formed by linking with the benzene ring and the nitrogen atom
  • L 1C represents an electron transfer-linking group containing at least one hetero ring selected from the group consisting of a thiophene ring, a furane ring, a pyrrole ring, a selenophene ring, and a hetero ring in which at least two of those are condensed with each other
  • R 1C and R 3C each independently represent a hydrogen atom or a substituent
  • R 2C represents a hydrogen atom or a substituent
  • B 1C represents a heterocyclic acidic nucleus, or a methylene group substituted with an electron-withdrawing group
  • B 1C represents a group having at least one acidic group
  • n1 represents an integer of 1 to 12.
  • X represents a group of non-metallic atoms necessary for forming a 6- or 7-membered nitrogen-containing heterocycle by linking with the benzene rings and the nitrogen atom;
  • L 1C , R 1C , R 2C , R 3C , B 1C and n1 each have the same meaning as those in formula (1C), respectively;
  • R 4C to R 7C each independently represent a hydrogen atom or a substituent; and
  • n2 represents an integer of 1 or 2.
  • X is a non-metallic atom for forming a 7-membered nitrogen-containing heterocycle by linking with the benzene rings and the nitrogen atom.
  • R 7C and R 9C each independently represent an aliphatic group, an aromatic group or a heterocyclic group (at least one functional group thereof may have an acidic group); m represents 0 or 1; the carbon-carbon double bond in formula (3C) may be any of an E-form or a Z-form; R 8C in formula (3C) represents a sulfur atom or a group represented by formula (5C); and the carbon-carbon double bond in formula (5C) may be any of an E-form or a Z-form;
  • R 10C and R 11C each independently represent a cyano group or an acidic group, and may be the same as or different from each other; and the carbon-carbon double bond in formula (4C) may be any of an E-form or a Z-form;
  • R 12C and R 13C each independently represent a cyano group or an acidic group, and may be the same as or different from each other; and the carbon-carbon double bond in formula (5C) may be any of an E-form or a Z-form.
  • R 9C represents an aliphatic group, an aromatic group or a heterocyclic group (each of which may have an acidic group).
  • R 7C represents an aliphatic group, an aromatic group or a heterocyclic group (each of which may have an acidic group).
  • a photoelectric conversion element comprising a light-receiving electrode
  • the light-receiving electrode comprises semiconductor fine particles sensitized by the dye described in any one of the items ⁇ 1c> to ⁇ 7c>.
  • the photoelectric conversion element described in the item ⁇ 8c> further comprising a porous material of insulation between the light-receiving electrode and a counter electrode.
  • a photoelectrochemical cell comprising the photoelectric conversion element described in any one of the above items ⁇ 8c> to ⁇ 10c>.
  • the dye of the first invention, the dye of the second invention and the dye of the third invention each have such favorable characteristics that high photoelectric conversion efficiency is obtained when the dye is used as a sensitizing dye for photoelectric conversion elements or photoelectrochemical cells.
  • each of the dyes does not make it necessary to use ruthenium in the sensitizing dye, photoelectric conversion elements or photoelectrochemical cells can be provided at a low cost.
  • the method of producing a dye according to the present invention makes it possible to suppress a by-product and resultantly to obtain the dye of the present invention with a favorable yield.
  • FIG. 1 is a cross-sectional view schematically showing an exemplary embodiment of the photoelectric conversion element according to the present invention.
  • the dye having a structure represented by any one of formula (1A) to (7A) for use in the first embodiment of the present invention will be explained.
  • the dye acts as a sensitizing dye for the photoelectrochemical cell of the present invention.
  • A represents a group of atoms necessary for forming a ring together with the carbon-nitrogen bond.
  • a preferred example of the ring formed by A is a residue obtained by eliminating a carbonyl group or a thiocarbonyl group from a heterocyclic acidic nucleus.
  • the heterocyclic acidic nucleus include those described in, for example, T. H. James, “The Theory of the Photographic Process, 4th edition”, Macmillan publishing, 1977, p. 199.
  • More preferred examples of the ring formed by A include residues obtained by eliminating a carbonyl group or a thiocarbonyl group from rhodanine, hydantoin, thiohydantoin, barbituric acid, thiobarbituric acid, pyrazolidinedione, pyrazolone, indanedione or isoxazolone; even more preferred examples include residues obtained by eliminating a carbonyl group or a thiocarbonyl group from rhodanine, hydantoin, thiohydantoin, barbituric acid or thiobarbituric acid; and a particularly preferred example is residues obtained by eliminating a carbonyl group or a thiocarbonyl group from rhodanine.
  • At least one of Y 1A and Y 2A represents an acidic group, and when both of them represent an acidic group, they may be the same as or different from each other. When only one of them is an acidic group, the other one represents an electron-withdrawing group.
  • Y 3A represents an acidic group.
  • the term “acidic group” means a group in which the pKa value of the most acidic hydrogen atom among the hydrogen atoms constituting the acidic group is 13 or less.
  • the acidic group include a carboxylic acid group (a carboxyl group), a sulfonic acid group, a phosphonic acid group, a phenolic hydroxyl group, an alkylsulfonylcarbamoyl group and a phosphoric acid group.
  • Preferred examples include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group and a phenolic hydroxyl group; more preferred examples include a carboxylic acid group and a sulfonic acid group; and particularly preferred examples include a carboxylic acid group.
  • the electron-withdrawing group may be a substituent having the effects described below ( ⁇ I effect and ⁇ M effect).
  • ⁇ I effect and ⁇ M effect In general, an electron-withdrawing group attenuates the electron density at a particular position of a molecule.
  • the electron-withdrawing property or electron-donating property cannot be explained only by the difference in the electronegativity. That is, since an excitation effect, a mesomeric effect and the like work together in a compositive manner, the manifestation of the electron-withdrawing property or the electron-donating property can vary with the aromaticity, presence of a conjugated system, or a topological positional relationship.
  • the electron-withdrawing effect is referred to as the ⁇ I effect
  • the electron-donating effect is referred to as the +I effect
  • an anion exhibits the +I effect
  • a cation exhibits the ⁇ I effect
  • the electron-withdrawing effect is referred to as the ⁇ M effect
  • the electron-donating effect is referred to as the +M effect. Examples of the electron-withdrawing group are shown below.
  • Preferred examples of the electron-withdrawing group include a cyano group, a nitro group, a sulfonyl group, a sulfoxy group, an acyl group, an alkoxycarbonyl group and a carbamoyl group; more preferred examples include a cyano group, a nitro group and a sulfonyl group; and a particularly preferred example is a cyano group.
  • one of Y 1A and Y 2A is a carboxylic acid group and the other is a cyano group.
  • acidity of the carboxylic acid group that is an acid group can be increased by an electron-withdrawing effect due to a cyano group.
  • the photoelectric conversion element containing semiconductor fine particles sensitized with the dye can exhibit high photoelectric conversion efficiency.
  • D represents a group to give a dye.
  • group to give a dye means a group of atoms necessary for constituting a dye as a whole, together with the structure other than Y in the formula (1A).
  • the dye formed by Y include polymethine dyes such as merocyanine, hemicyanine, styryl, oxonol and cyanine; diarylmethines including acridine, xanthene, and thioxanthene; triarylmethine, coumarin, indoaniline, indophenol, diazine, oxazine, thiazine, diketopyrrolopyrrole, indigo, anthraquinone, perylene, quinacridone, naphthoquinone, bipyridyl, terpyridyl, tetrapyridyl, and phenanthroline.
  • Preferred examples include polymethine dyes and
  • n represents an integer of 1 or greater, and is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1.
  • L represents a single bond or a divalent linking group, and L is preferably a single bond or a divalent linking group.
  • the divalent linking group is not particularly limited, but is preferably a divalent linking group having 0 to 30 carbon atoms, for example, an alkylene group and an arylene group.
  • the divalent linking group may also contain a heteroatom(s).
  • Preferred examples of L include methylene, ethylene, propylene, phenylene and ethenylene.
  • R A , R 1A , R 2A and R 3A in the formulas (2A) to (7A) each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group linked through a carbon atom.
  • Preferred examples include an aliphatic group and an aromatic group, and a particularly preferred example is an aliphatic group.
  • R 3A is preferably a hydrogen atom.
  • Examples of the aliphatic group include an alkyl group (e.g. methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, or 2-ethylhexyl), and a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, e.g. cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl).
  • alkyl group e.g. methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, or 2-ethylhexyl
  • Preferred examples of the aliphatic group include an alkyl group and an alkenyl group, each having 1 to 30 carbon atoms (preferably having 1 to 25 carbon atoms, more preferably having 1 to 20 carbon atoms), and the aliphatic group may be substituted.
  • aromatic group examples include a benzene ring, a furan ring, a pyrrole ring, a pyridine ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a pyrimidine ring, a pyrazine ring, or rings formed by condensation of the foregoing rings. These groups may be substituted.
  • Preferred examples include a benzene ring, a pyrrole ring, a pyridine ring and a thiophene ring; more preferred examples include a benzene ring and a thiophene ring; and a particularly preferred example is a benzene ring. These groups may be substituted.
  • the heterocyclic group linked through a carbon atom is preferably a 3- to 6-membered substituted or unsubstituted heterocyclic group, more preferably a 5- or 6-membered unsubstituted heterocyclic group, and particularly preferably a 6-membered heterocyclic group (for example, piperidine or morpholine). These groups may be substituted.
  • LL represents at least one divalent linking group selected from the group consisting of an alkenylene group, an alkynylene group and an arylene group. LL may be a combination of these groups, and may also be substituted.
  • the alkenylene group include ethenylene.
  • Preferred examples the alkynylene group include ethynylene.
  • Preferred examples of the arylene group include a benzene ring, a furan ring, and a pyrrole ring, or divalent rings formed by condensation of the foregoing rings.
  • Examples of LL include those groups represented by any one of the formulas shown below. Among the formulas shown below, L-a, L-b, L-c or L-e is preferable; L-a, L-b or L-e is more preferable; and L-b is particularly preferable.
  • B represents a group of atoms necessary for forming a ring together with the two carbon atoms and the nitrogen atom on the benzene ring.
  • the acidic group (for example, a carboxylic acid group, a phosphonic acid group or a sulfonic acid group) in formulas (1A) to (7A) may be dissociated and have a counter cation.
  • the counter cation is not particularly limited, and may be any of an organic cation and an inorganic cation.
  • Representative examples include an alkali metal ion (lithium, sodium, potassium, or the like), an alkaline earth metal ion (magnesium, calcium or the like), and cations of ammonium, alkylammonium (for example, diethylammonium, or tetrabutylammonium), pyridinium, alkylpyridinium (for example, methylpyridinium), guanidium and tetraalkylphosphonium.
  • alkylammonium for example, diethylammonium, or tetrabutylammonium
  • pyridinium for example, diethylammonium, or tetrabutylammonium
  • alkylpyridinium for example, methylpyridinium
  • guanidium and tetraalkylphosphonium for example, methylpyridinium
  • the dye may have an appropriate substituent (hereinafter, referred to as substituent W A ).
  • substituent W A include: a halogen atom (e.g. a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group [which represents a substituted or unsubstituted linear, branched, or cyclic alkyl group, and which includes an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, e.g.
  • a cyclohexyl group a cyclopentyl group, or a 4-n-dodecylcyclohexyl group
  • a bicycloalkyl group preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, i.e. a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, e.g. a bicyclo[1.2.2]heptan-2-yl group or a bicyclo[2.2.2]octan-3-yl group), and a tricyclo or higher structure having three or more ring structures; and an alkyl group in substituents described below (e.g.
  • an alkyl group in an alkylthio group represents such an alkyl group of the above concept]; an alkenyl group [which represents a substituted or unsubstituted linear, branched, or cyclic alkenyl group, and which includes an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, e.g. a vinyl group, an allyl group, a prenyl group, a geranyl group, or an oleyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, i.e.
  • a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms e.g. a 2-cyclopenten-1-yl group or a 2-cyclohexen-1-yl group
  • a bicycloalkenyl group which represents a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, i.e. a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond, e.g.
  • a phenyl group a p-tolyl group, a naphthyl group, an m-chlorophenyl group, or an o-hexadecanoylaminophenyl group
  • an aromatic group e.g.
  • a benzene ring a furan ring, a pyrrole ring, a pyridine ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a pyrimidine ring, a pyrazine ring, or rings formed by condensation of the foregoing rings); a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted 5- or 6-membered aromatic or nonaromatic heterocyclic compound; more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, e.g.
  • a trimethylsilyloxy group or a t-butyldimethylsilyloxy group a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, e.g. a 1-phenyltetrazol-5-oxy group or a 2-tetrahydropyranyloxy group); an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, e.g.
  • a formyloxy group an acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, or a p-methoxyphenylcarbonyloxy group
  • a carbamoyloxy group preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, e.g.
  • a methoxycarbonyloxy group a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group
  • an aryloxycarbonyloxy group preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, e.g.
  • a phenoxycarbonyloxy group a p-methoxyphenoxycarbonyloxy group, or a p-n-hexadecyloxyphenoxycarbonyloxy group
  • an amino group preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, e.g.
  • an amino group preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, e.g.
  • a formylamino group an acetylamino group, a pivaloylamino group, a lauroylamino group, a benzoylamino group, or a 3,4,5-tri-n-octyloxyphenylcarbonylamino group
  • an aminocarbonylamino group preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, e.g.
  • a carbamoylamino group an N,N-dimethylaminocarbonylamino group, an N,N-diethylaminocarbonylamino group, or a morpholinocarbonylamino group
  • an alkoxycarbonylamino group preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, e.g.
  • a methoxycarbonylamino group a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, or an N-methyl-methoxycarbonylamino group
  • an aryloxycarbonylamino group preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, e.g.
  • a phenoxycarbonylamino group a p-chlorophenoxycarbonylamino group, or an m-n-octyloxyphenoxycarbonylamino group
  • a sulfamoylamino group preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, e.g.
  • a sulfamoylamino group an N,N-dimethylaminosulfonylamino group, or an N-n-octylaminosulfonylamino group
  • an alkyl- or aryl-sulfonylamino group preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, e.g.
  • a methylsulfonylamino group a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, or a p-methylphenylsulfonylamino group
  • a mercapto group an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, e.g.
  • a 2-benzothiazolylthio group or a 1-phenyltetrazol-5-ylthio group a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, e.g.
  • a methylsulfinyl group an ethylsulfinyl group, a phenylsulfinyl group, or a p-methylphenylsulfinyl group
  • an alkyl- or aryl-sulfonyl group preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, e.g.
  • a methylsulfonyl group a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, or a p-methylphenylsulfonyl group
  • an acyl group preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic carbonyl group having 4 to 30 carbon atoms, which is bonded to said carbonyl group through a carbon atom, e.g.
  • an acetyl group a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a p-n-octyloxyphenylcarbonyl group, a 2-pyridylcarbonyl group, or a 2-furylcarbonyl group); an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, e.g.
  • a phenoxycarbonyl group preferably an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, or a p-t-butylphenoxycarbonyl group
  • an alkoxycarbonyl group preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, e.g. a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, or an n-octadecyloxycarbonyl group
  • a carbamoyl group preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, e.g.
  • a carbamoyl group an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N,N-di-n-octylcarbamoyl group, or an N-(methylsulfonyl)carbamoyl group); an aryl- or heterocyclic-azo group (preferably a substituted or unsubstituted aryl azo group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, e.g.
  • a phenylazo group a p-chlorophenylazo group, or a 5-ethylthio-1,3,4-thiadiazol-2-ylazo group
  • an imido group preferably an N-succinimido group or an N-phthalimido group
  • a phosphino group preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, e.g.
  • a dimethylphosphino group a diphenylphosphino group, or a methylphenoxyphosphino group
  • a phosphinyl group preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, e.g. a phosphinyl group, a dioctyloxyphosphinyl group, or a diethoxyphosphinyl group
  • a phosphinyloxy group preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, e.g.
  • a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group
  • a phosphinylamino group preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, e.g. a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group
  • a silyl group preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, e.g. a trimethylsilyl group, a t-butyldimethylsilyl group, or a phenyldimethylsilyl group).
  • the substituent may be further substituted.
  • examples of the substituent include the substituent W A mentioned above.
  • the dye (dye compound) having at least one structure represented by any one of formulae (1A) to (7A) can be synthesized by, for example, methods described or cited in F. M. Harmer, “Heterocyclic Compounds—Cyanine Dyes and Related Compounds”, John Wiley & Sons, New York and London, 1994, or methods similar thereto.
  • the dye (dye compound) having at least one of the structures represented by any of the above-described formulae (1A) to (7A) is preferably produced according to a method which includes a process of obtaining a dye having the above-described formula (1A) by deprotecting of at least one of Z 1A , Z 2A and Z 3A that is a substituent represented by formula (9A) in the compound represented by formula (8A), in the presence of a transition metal catalyst.
  • A, D, n and L each have the same meaning as those in formula (1A), respectively; at lease one of Z 1A , Z 2A and Z 3A represents a substituent represented by formula (9A); and when each of Z 1A , Z 2A and Z 3A is not the substituent represented by formula (9A), each represent an acidic group, in which any one of Z 1A and Z 2A represents an electron-withdrawing group.
  • the acidic group that is represented by the Z 1A , Z 2A or Z 3A is such acidic group that the pKa value of the most acidic hydrogen atom among the hydrogen atoms constituting the acidic group is 13 or less.
  • the acidic group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phenolic hydroxyl group, an alkylsulfonylcarbamoyl group and a phosphoric acid group.
  • Preferred examples include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group and a phenolic hydroxyl group; more preferred examples include a carboxylic acid group and a sulfonic acid group; and particularly preferred examples include a carboxylic acid group.
  • Z 1A , Z 2A or Z 3A represents neither the substituent group represented by formula (9A) nor the acidic group, but represents an electron-withdrawing group
  • examples of the electron-withdrawing group include substituent groups having the ⁇ I effect and substituent groups having the ⁇ M effect as described above.
  • the electron-withdrawing group is preferably a cyano group, a nitro group, a sulfonyl group, a sulfoxy group, an acyl group, an alkoxycarbonyl group or a carbamoyl group; further preferably a cyano group, a nitro group or a sulfonyl group; and particularly preferably a cyano group.
  • the compound represented by formula (8A) can be synthesized with reference to literatures. For example, it can be synthesized by methods described or cited in F. M. Harmer, “Heterocyclic Compounds—Cyanine Dyes and Related Compounds”, John Wiley & Sons, New York and London, 1994, or methods similar thereto.
  • transition metals that are used for a method of producing the dye having the structure represented by formula (1A) from a compound represented by formula (8A) in the presence of the transition metal catalyst, nickel, palladium, molybdenum, and ruthenium are preferred, and palladium is more preferred.
  • a form of palladium is not particularly limited as long as it is a palladium compound.
  • the palladium compound include tetravalent palladium compounds such as sodium hexachloropalladate (IV) tetrahydrate, and potassium hexachloropalladate (IV); divalent palladium compounds such as palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, palladium (II) acetate, palladium acetylacetonate (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium (II), and dichlorobis (triphenylphosphine) palladium (II); and zero-valent palladium compounds such as tetrakistriphenylphosphine palladium, bis(dibenzylidene) palladium, tris (dibenzylidene) dipall
  • a use amount of the above-described palladium compound is not particularly limited.
  • the use amount thereof is generally from 0.00001 to 0.1 mole times, and preferably from 0.0001 to 0.05 mole times as much as the compound represented by formula (8A).
  • a dye having the structure represented by the above-described formula (1A) can be produced in good yield in the case where a tertiary phosphorus compound is used as a ligand.
  • the tertiary phosphorus compound is not particularly limited.
  • Examples of the tertiary phosphorus compound include triphenylphosphine, triorthtolylphosphine, diphenylphosphinoferrocene, tri n-butylphosphine, triisobutylphosphine, tri sec-butylphosphine, tri tert-butylphosphine, 1,1′-bis(di-t-butylphosphino)ferrocene, 1,3-bis (di-t-butylphosphino) propane, 1,4-bis(di-t-butylphosphino) butane, and 1,5-bis(di-t-butylphosphino) pentane.
  • the tertiary phosphorus compound may be a form in which the tertiary phosphorus compound has already coordinated to a metal catalyst, namely a metal complex.
  • a use amount of the tertiary phosphorus compound is generally from 0.01 to 20 mole times, and preferably from 0.5 to 10.0 mole times as much as one palladium atom of the palladium compound.
  • a base is used in order to neutralize an acid that is generated as a by-product.
  • the base any of inorganic bases and organic bases may be used.
  • Examples of the inorganic bases include: carbonates such as cesium carbonate, potassium carbonate, sodium carbonate, and lithium carbonate; acetates such as potassium acetate, sodium acetate, and lithium acetate; hydrogen carbonates such as potassium hydrogen carbonate, sodium hydrogen carbonate, and lithium hydrogen carbonate; sulfates such as potassium sulfate, sodium sulfate, and lithium sulfate; hydrogen sulfates such as potassium hydrogen sulfate, sodium hydrogen sulfate, and lithium hydrogen sulfate; phosphates such as potassium phosphate, sodium phosphate, and lithium phosphate; and tert-butoxide salts such as potassium tert-butoxide, sodium tert-butoxide, and lithium tert-butoxide.
  • carbonates such as cesium carbonate, potassium carbonate, sodium carbonate, and lithium carbonate
  • acetates such as potassium acetate, sodium acetate, and lithium acetate
  • hydrogen carbonates such as potassium hydrogen carbon
  • organic bases tertiary amines are ordinarily used.
  • examples of the organic bases include morpholine, triethylamine, tributylamine, trihexylamine, triisopropylamine, diisopropylethylamine, N-methylmorpholine, N-ethylmorpholine, tricyclohexylamine, and pyridine.
  • a preferable base is inorganic bases, and more preferably tert-butoxide salts.
  • a use amount of the base is not particularly limited, as long as the amount thereof is 4.0 or more mole times as much as compound (3), since a theoretical amount thereof is 4.0 mole times as much as the compound (3).
  • the amount thereof is preferably from 4.0 to 40.0 mole times, and more preferably from 4.0 to 20.0 mole times.
  • Examples of a solvent used for the reaction include: hydrocarbon type solvents such as benzene, toluene, n-hexane, and cyclohexane; ether type solvents such as diethyl ether, tetrahydrofurane (THF), 1,4-dioxane, tert-butylmethyl ether (MTBE), dimethoxyethane, and ethyleneglycol dimethylether; halogen type solvents such as methylene chloride, chloroform, 1,1,1-trichloroethane, and chlorobenzene; amide type solvents such as dimethylformamide (DMF), and N-methylpyrrolidone (NMP); sulfoxide type solvents such as dimethylsulfoxide (DMSO); phosphoramide type solvents such as hexamethylphosphoramide (HMPA), and hexamethylphosphoroustriamide (HMPT).
  • hydrocarbon type solvents and ether type solvents are preferred.
  • This reaction is preferably performed under the inert gas atmosphere such as nitrogen, helium, or argon.
  • the reaction may be performed under ordinary pressure, or increased pressure.
  • each of these compounds may be added to a reactor in an arbitrary order.
  • a palladium compound and the tertiary phosphorous compound are mixed in advance, and then other compounds may be added in an arbitrary order.
  • the reaction temperature though depends on the kind of the base and the solvent used for the reaction, is ordinarily from 20° C. to 250° C., and preferably from 20° C. to 180° C.
  • the reaction time though depends on the reaction temperature and the use amount of a transition metal catalyst used for the reaction, is ordinarily from 30 minutes to 48 hours, and preferably from 1 to 24 hours.
  • allyl cyanoacetate in which a protective group is an allyl group is prepared as one of starting compounds.
  • Compound D-1-b can be obtained while the allyl group of the protective group is kept as it is.
  • the Compound D-1-b is allowed to react with Compound D-1-e that is separately prepared.
  • the Exemplified dye D-1 can be obtained by deprotection in the presence of tetrakistriphenylphosphine palladium.
  • the dye of the first embodiment of the present invention is produced by the production method of the present invention, by-products are very few. As a result, a photoelectric conversion element containing semiconductor fine particles sensitized with the dye prepared by the production method of the present invention can exhibit high photoelectric conversion efficiency. Further, in the case where a dye is produced by the production method of the present invention, a tiny amount of the compound that is protected by a protective group represented by the above-described formula (8A) remains in the dye. The thus-produced dye compound has little or no adverse effect on photoelectric conversion efficiency, when a photoelectric conversion element is produced by using the dye. It is acceptable for the compound represented by the formula (8A) to be contained in an amount of 10 ppm or more. However, when the content of the compound is too much, there is a possibility of the adverse effect on photoelectric conversion efficiency. Accordingly, the content of the compound represented by the formula (8A) is preferably 50 ppm or less, and more preferably 20 ppm or less.
  • one-electron oxidation state of the dye is stabilized by introducing a donor site having a widespread conjugation system.
  • structure that actively promotes a J-association means a molecular structure that aligns a group having hydrophobicity and high affinity for electrolyte, such as a long-chain alkyl group or an aryl group, at the position of the opposite side to an anchor site such as a COOH group, and in addition, a structure that promotes alignment of the Brickstone structure, the Staircase structure, or the Ladder structure by imparting high planarity to a dye molecule, and introducing therein such a substituent group that is capable of sterically protruding from a plane at a center of molecular conjugated plane, or alternatively by producing the same effects as those described above by distortion of a molecule or the like.
  • the dye of the second embodiment of the present invention has a structure represented by formula (1B).
  • X represents a group of non-metallic atoms necessary for forming a nitrogen-containing 7-membered ring by linking with the benzene rings.
  • group of non-metallic atoms means a group of atoms bonded by at least one kind of member selected from the group consisting of carbon, oxygen, nitrogen and sulfur atoms.
  • Y represents a group to give a dye.
  • group to give a dye means a group of atoms necessary for constituting a dye as a whole, together with the structure other than Y in formula (1B).
  • the dye formed by Y include polymethine dyes such as merocyanine, hemicyanine, styryl, oxonol and cyanine; diarylmethines such as acridine, xanthene, and thioxanthene; triarylmethine, coumarin, indoaniline, indophenol, diazine, oxazine, thiazine, diketopyrrolopyrrole, indigo, anthraquinone, perylene, quinacridone, naphthoquinone, bipyridyl, terpyridyl, tetrapyridyl, and phenanthroline.
  • Preferred examples include polymethine
  • Z represents a substituent, and examples thereof include an aliphatic group, an aromatic group, a heterocyclic group or the like.
  • substituents include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a heterocyclic ring.
  • Preferred examples include an alkyl group (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, or benzyl), a substituted aryl group (for example, phenyl, tolyl, or naphthyl), and an alkoxy group (for example, methoxy, ethoxy, isopropoxy or butoxy).
  • alkyl group for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, or benzyl
  • a substituted aryl group for example, phenyl, tolyl, or naphthyl
  • an alkoxy group for example, methoxy, e
  • n 0 or a positive integer.
  • the substituents represented by Z may be the same as or different from each other, when m is 2 or more.
  • R 1B represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group that is linked via a carbon atom.
  • R 1B include a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl or benzyl), a substituted or unsubstituted aryl group (for example, phenyl, tolyl or naphthyl), and a substituted or unsubstituted heterocyclic residue (for example, pyridyl, imidazolyl, furyl, thienyl, oxazolyl, thiazolyl, benzimidazolyl, or quinolyl).
  • R 1B is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, or benzyl).
  • X represents a group of non-metallic atoms necessary for forming a nitrogen-containing 7-membered ring by linking with the benzene rings.
  • group of non-metallic atoms means a group of atoms bonded by at least one kind of atoms selected from the group consisting of carbon, oxygen, nitrogen and sulfur atoms.
  • R 1B represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group that is linked via a carbon atom.
  • R 1B include a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl or benzyl), a substituted or unsubstituted aryl group (for example, phenyl, tolyl or naphthyl), and a substituted or unsubstituted heterocyclic residue (for example, pyridyl, imidazolyl, furyl, thienyl, oxazolyl, thiazolyl, benzimidazolyl, or quinolyl).
  • a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms for example, methyl, ethyl, n-butyl, n-hexyl, iso
  • R 1B include a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, or benzyl).
  • R 2B to R 9B each independently represent a hydrogen atom or a substituent, and at least one substituent of R 2B to R 9B represents a group to give a dye represented by formula (3B).
  • substituents include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group and a heterocyclic group.
  • Preferred examples include an alkyl group (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, or benzyl), a substituted aryl group (for example, phenyl, tolyl or naphthyl), and an alkoxy group (for example, methoxy, ethoxy, isopropoxy, or butoxy).
  • R 12B represents a group having at least one acidic group, or an acidic nucleus substituted with at least one acidic group.
  • acidic nucleus examples include those described in, for example, T. H. James, “The Theory of the Photographic Process, 4th edition”, Macmillan publishing, 1977, p. 199.
  • R 12B has at least one acidic group
  • R 12B simultaneously has an electron-withdrawing group
  • the electron-withdrawing group may be a substituent having the effects described below ( ⁇ I effect and ⁇ M effect).
  • the type or bonding position of the electron-withdrawing group is appropriately selected so as to exhibit an effect that the overlap of the molecular orbital in the excited state of the dye and the light-receiving electrode seems to increase.
  • an electron-withdrawing group attenuates the electron density at a particular position of a molecule.
  • the electron-withdrawing property or electron-donating property cannot be explained only by the difference in the electronegativity. That is, since an excitation effect, a mesomeric effect and the like work together in a compositive manner, the manifestation of the electron-withdrawing property or the electron-donating property can vary with the aromaticity, presence of a conjugated system, or a topological positional relationship.
  • Hammett's rule As an experimental rule for quantitatively evaluating and predicting these effects on the basis of the acid dissociation constant of para- and meta-substituted benzoic acid.
  • the electron-withdrawing effect is referred to as the ⁇ I effect
  • the electron-donating effect is referred to as the +I effect
  • an atom having higher electronegativity than carbon exhibits the ⁇ I effect
  • an anion exhibits the +I effect
  • a cation exhibits the ⁇ I effect
  • the electron-withdrawing effect is referred to as the ⁇ M effect
  • the electron-donating effect is referred to as the +M effect. Examples of the electron-withdrawing group are shown below.
  • the acidic nucleus include a rhodanine nucleus, hydantoin, thiohydantoin, barbituric acid, pyrazolidinedione, pyrazolone, and indanedione. These may contain two or more acidic nuclei linked together, with each acidic nucleus having been dehydrated and condensed at the carbonyl moiety.
  • Preferred examples include rhodanine, hydantoin, thiohydantoin, barbituric acid and pyrazolidinedione, and rhodanine is particularly preferred among them.
  • the acidic group contained in R 12B represents a proton-dissociative group having a pKa of 13 or lower.
  • Specific preferred examples of the acidic group include a carboxylic acid, a sulfonic acid, a phosphoric acid and a phosphoric acid ester.
  • a more preferred example of the acidic group is a carboxylic acid.
  • the carbon-carbon double bond may be any of an E-form double bond and a Z-form double bond.
  • R 10B , R 11B and R 13B each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. r represents an integer of 0 or more.
  • the carbon-carbon double bond in formula (3B) may be any of an E-form double bond and a Z-form double bond.
  • R 10B , R 11B and R 13B each are preferably a hydrogen atom, an aliphatic group or an aromatic group; more preferably an aliphatic group or an aromatic group.
  • the dye represented by formula (4B) is a dye where X in formula (1B) represents an ethylene group, and a nitrogen-containing 7-membered ring structure has been formed thereby. Furthermore, one of the benzene rings substituted with a nitrogen atom has one group to give a dye at the para-position.
  • the dye represented by formula (5B) has a carbon-carbon double bond in the nitrogen-containing 7-membered ring, and has a group to give a dye on the nitrogen-containing 7-membered ring.
  • R 14B represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, or a heterocyclic group.
  • R 14B is preferably an alkyl group (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl or benzyl), a substituted aryl group (for example, phenyl, tolyl or naphthyl), or an alkoxy group (for example, methoxy, ethoxy, isopropoxy or butoxy).
  • alkyl group for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl or benzyl
  • a substituted aryl group for example, phenyl, tolyl or naphthyl
  • an alkoxy group for example, methoxy, ethoxy
  • the dye represented by formula (6B) is a dye where X in formula (1B) represents an ethylene group, and a nitrogen-containing 7-membered ring structure has been formed thereby. Each of the two benzene rings substituted with a nitrogen atom has one group to give a dye at the para-position.
  • R 12B may be a group represented by formula (7B) or formula (8B).
  • R 15B and R 16B each independently represent an aliphatic group, an aromatic group or a heterocyclic group (at least one functional group thereof may have an acidic group). 1 represents 0 or 1.
  • the carbon-carbon double bond in formula (7) may be any of an E-form double bond and a Z-form double bond.
  • R 17B in formula (7) represents a sulfur atom or a group represented by formula (9).
  • R 15B and R 16B are preferably an aliphatic group, an aromatic group or a heterocyclic group, each having an acidic group, and R 15 and R 16 may be different from each other.
  • Specific preferred examples of the acidic group include carboxylic acid, sulfonic acid, phosphoric acid, a phosphoric acid ester, and the like.
  • a more preferred example of the acidic group is carboxylic acid.
  • the carbon-carbon double bond in formula (7) may be any of an E-form double bond and a Z-form double bond.
  • R 20B and R 21B each independently represents a cyano group or an acidic group, and R 20B and R 21B may be the same as or different from each other.
  • Specific preferred examples of the acidic group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid ester group, and the like.
  • a more preferred example of the acidic group is a carboxylic acid group.
  • the carbon-carbon double bond in formula (9B) may be any of an E-form double bond and a Z-form double bond.
  • R 18B and R 19B each independently represent a cyano group or an acidic group, and R 18B and R 19B may be the same as or different from each other.
  • Specific preferred examples of the acidic group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid ester group, and the like.
  • a more preferred example of the acidic group is a carboxylic acid group.
  • the carbon-carbon double bond in formula (8B) may be any of an E-form double bond and a Z-form double bond.
  • the group represented by formula (7B) may be a group represented by formula (10B).
  • R 16B represents an aliphatic group, an aromatic group or a heterocyclic group, each of which may have an acidic group.
  • R 12B may be a group represented by formula (11B).
  • R 15B represents an aliphatic group, an aromatic group or a heterocyclic group (each of which may have an acidic group).
  • R 12B may be a group represented by formula (12B).
  • the dye of the first embodiment of the present invention has a maximum absorption wavelength in a solution in a range of preferably from 350 nm to 1,000 nm, more preferably from 370 nm to 700 nm, and still more preferably from 390 nm to 650 nm.
  • the dye of the third embodiment of the present invention has a structure represented by formula (1C).
  • a 1 represents a 6- or 7-membered nitrogen-containing heterocycle formed by linking with the benzene ring.
  • the 6-membered or 7-membered nitrogen-containing heterocycle represented by A 1 preferably include: a 6-membered or 7-membered nitrogen-containing heterocycle that is formed by at least one kind atom selected from the group consisting of a carbon atom, a sulfur atom and an oxygen atom, in addition to a nitrogen atom; more preferably a 6-membered or 7-membered nitrogen-containing heterocycle that is formed by at least one kind atom selected from the group consisting of a carbon atom and a sulfur atom, in addition to a nitrogen atom; and especially more preferably a 7-membered nitrogen-containing heterocycle that is formed by only carbon atom(s) in addition to a nitrogen atom.
  • a 1 may be a condensed ring or a substituted ring. Further, A 1 may have a substituent. Examples of the condensed ring include a ring condensed with a benzene ring, a pyridine ring, a pyrrol ring, a furane ring, and a thiophene ring.
  • L 1C represents an electron transfer-linking group containing at least one hetero ring selected from the group consisting of a thiophene ring, a furane ring, a pyrrole ring, a selenophene ring, and a hetero ring in which at least two of those are condensed with each other.
  • L 1C is preferably an electron transfer-linking group containing at least one kind of hetero rings selected from the group consisting of a thiophene ring, a pyrrol ring, and a hetero ring condensed thereof, and more preferably an electron transfer-linking group containing at least one kind of hetero rings selected from a thiophene ring, or a heterocyclic ring condensed thereof.
  • the condensed rings include heterocyclic rings condensed with a benzene ring, a pyridine ring, a pyrrol ring, a furane ring, a thiophene ring, or the like.
  • R 1C and R 3C each independently represent a hydrogen atom or a substituent.
  • R 1C and R 3C each are preferably at least one kind of substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group and an aryl group; further preferably at least one kind of substituent selected from the group consisting of an alkyl group, an alkoxy group and an aryl group; particularly preferably at least one kind of substituent selected from the group consisting of an alkyl group and an aryl group; and further preferably an alkyl group.
  • R 1C and R 3C each represent an alkyl group
  • preferred examples of the alkyl group include a substituted or unsubstituted linear, branched, or cyclic alkyl group, and which includes an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, e.g.
  • a cycloalkyl group preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, e.g.
  • cyclohexyl cyclopentyl, or 4-n-dodecylcyclohexyl
  • a bicycloalkyl group preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, i.e. a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, e.g. bicyclo[1,2,2]heptan-2-yl or a bicyclo[2,2,2]octan-3-yl
  • a tricyclo or higher structure having three or more ring structures.
  • alkyl group examples include an alkyl group having 1 to 30 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, or 2-ethylhexyl) and a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, e.g.
  • cyclohexyl cyclopentyl, or 4-n-dodecylcyclohexyl
  • particularly preferred examples include an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl and 2-ethylhexyl.
  • R 1C and R 3C represents an aryl group
  • preferred examples of the aryl group include a phenyl group, a naphthyl group, a thienyl group, a furyl group, a pyrryl group, or condensed rings of these groups; and especially preferably a phenyl group, a thienyl group, or condensed rings of these groups.
  • the condensed ring include a benzene ring, a pyridine ring, a pyrrol ring, a furane ring, and a thiophene ring.
  • R 1C and R 3C each represent an alkoxy group
  • preferred examples of the alkoxy group include a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, e.g. methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy or 2-methoxyethoxy; further preferred examples include a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, e.g. methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy or 2-methoxyethoxy; and particularly preferred examples include a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
  • R 2C represents a hydrogen atom or a substituent.
  • R 2C is preferably a hydrogen atom.
  • examples of the substituent include the substituent W C described below.
  • Preferred examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aromatic group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alky
  • an alkyl group an alkenyl group, an alkynyl group, an aromatic group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl- or aryl-sulfinyl group, an alkyl- or aryl-sulfonyl group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.
  • Particularly preferred examples include an alkyl group, an alkenyl group, an alkynyl group, an aromatic group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and a heterocyclic thio group.
  • B 1C represents a heterocyclic acidic nucleus, or a methylene group substituted with an electron-withdrawing group; and B 1C has at least one acidic group.
  • heterocyclic acidic nucleus include those described in, for example, T. H. James, “The Theory of the Photographic Process, 4th edition”, Macmillan publishing, 1977, p. 199.
  • heterocyclic acidic nucleus More preferred examples include rhodanine, hydantoin, thiohydantoin, barbituric acid, thiobarbituric acid, pyrazolidinedione, pyrazolone, indanedione or isoxazolone; even more preferred examples include rhodanine, hydantoin, thiohydantoin, barbituric acid or thiobarbituric acid; and a particularly preferred example is rhodanine.
  • B 1C is a methylene group substituted with an electron-withdrawing group
  • examples of the electron-withdrawing group include substituents having the following effects.
  • an electron-withdrawing group attenuates the electron density at a particular position of a molecule.
  • the electron-withdrawing property or electron-donating property cannot be explained only by the difference in the electronegativity. That is, since an excitation effect, a mesomeric effect and the like work together in a compositive manner, the manifestation of the electron-withdrawing property or the electron-donating property can vary with the aromaticity, presence of a conjugated system, or a topological positional relationship.
  • Hammett's rule As an experimental rule for quantitatively evaluating and predicting these effects on the basis of the acid dissociation constant of para- and meta-substituted benzoic acid.
  • the electron-withdrawing effect is referred to as the ⁇ I effect
  • the electron-donating effect is referred to as the +I effect
  • an atom having higher electronegativity than carbon exhibits the ⁇ I effect
  • an anion exhibits the +I effect
  • a cation exhibits the ⁇ I effect
  • the electron-withdrawing effect is referred to as the ⁇ M effect
  • the electron-donating effect is referred to as the +M effect. Examples of the electron-withdrawing group are shown below.
  • Preferred examples of the electron-withdrawing group include a cyano group, a nitro group, a sulfonyl group, a sulfoxy group, an acyl group, an alkoxycarbonyl group and a carbamoyl group; more preferred examples include a cyano group, a nitro group and a sulfonyl group; and a particularly preferred example is a cyano group.
  • a heterocyclic ring acidic nucleus or a methylene group substituted with an electron-withdrawing group each of which has at least one acidic group.
  • the term “acidic group” means a group in which the pKa value of the most acidic hydrogen atom among the hydrogen atoms constituting the acidic group is 13 or less.
  • the acidic group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phenolic hydroxyl group, an alkylsulfonylcarbamoyl group and a phosphoric acid group.
  • Preferred examples include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group and a phenolic hydroxyl group; more preferred examples include a carboxylic acid group and a sulfonic acid group; and particularly preferred examples include a carboxylic acid group.
  • n1 represents an integer of 1 to 12.
  • n1 is preferably an integer of 1 to 10; further preferably an integer of 2 to 8; and particularly preferably an integer of 2 to 6.
  • the dye represented by formula (1C) is preferably a dye represented by formula (2C).
  • X represents a group of atoms necessary for forming a 6- or 7-membered nitrogen-containing heterocycle by linking with the benzene rings.
  • group of non-metallic atoms means a group of atoms bonded by at least one kind of member selected from the group consisting of carbon, oxygen, nitrogen and sulfur atoms.
  • the 6-membered or 7-membered nitrogen-containing heterocycle represented by X preferably include a 6-membered or 7-membered nitrogen-containing heterocycle formed by at least one kind atom selected from a group consisting of a carbon atom, a sulfur atom and an oxygen atom, in addition to the nitrogen atom.
  • Preferred examples of the ring include a 6-membered or 7-membered nitrogen-containing heterocycle formed by at least one kind atom selected from a carbon atom and a sulfur atom, in addition to the nitrogen atom; especially preferred examples include a 7-membered nitrogen-containing heterocycle formed by at least one kind atom selected from the carbon atoms and a sulfur atom(s), in addition to the nitrogen atom; and further preferred examples include a 7-membered nitrogen-containing heterocycle formed by the carbon atoms and a sulfur atom(s), in addition to the nitrogen atom.
  • X may be a condensed ring or a substituted ring. Further, X may have a substituent group. Examples of the condensed ring include a benzene ring, a pyridine ring, a pyrrol ring, a furane ring, and a thiophene ring.
  • R 4C to R 7C each independently represent at least one kind of substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group and an aryl group.
  • R 4C to R 7C each are preferably a hydrogen atom or an alkyl group.
  • R 4C to R 7C each represent an alkyl group
  • preferred examples of the alkyl group include a substituted or unsubstituted linear, branched, or cyclic alkyl group, and which includes an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, e.g.
  • a cycloalkyl group preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, e.g.
  • cyclohexyl cyclopentyl, or 4-n-dodecylcyclohexyl
  • a bicycloalkyl group preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, i.e. a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, e.g. bicyclo[1,2,2]heptan-2-yl or a bicyclo[2,2,2]octan-3-yl
  • a tricyclo or higher structure having three or more ring structures.
  • alkyl group examples include an alkyl group having 1 to 30 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, or 2-ethylhexyl) and a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, e.g.
  • cyclohexyl cyclopentyl, or 4-n-dodecylcyclohexyl
  • particularly preferred examples include an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-hexyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl and 2-ethylhexyl.
  • each of R 3C to R 7C represents an aryl group
  • preferred examples of the aryl group include a phenyl group, a naphthyl group, a thienyl group, a furyl group, a pyrryl group, or condensed rings of these groups; and especially preferably a phenyl group, a thienyl group, or condensed rings of these groups.
  • the condensed ring include a benzene ring, a pyridine ring, a pyrrol ring, a furane ring, and a thiophene ring.
  • R 3C to R 7C each represent an alkoxy group
  • preferred examples of the alkoxy group include a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, e.g. methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy or 2-methoxyethoxy; further preferred examples include a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, e.g. methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy or 2-methoxyethoxy; and particularly preferred examples include a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.
  • n2 represents an integer of 1 or 2. n2 is preferably an integer of 2.
  • B 1C is preferably a group represented by formula (3C) or (4C).
  • R 7C and R 9C each independently represent an aliphatic group, an aromatic group or a heterocyclic group (at least one functional group thereof may have the acidic group described above).
  • R 7C and R 9C each are preferably an aliphatic group or an aromatic group; further preferably an aliphatic group or an aromatic group; and particularly preferably an aliphatic group.
  • Examples of the aliphatic group include an alkyl group (e.g. methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, or 2-ethylhexyl) and a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, e.g. cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl).
  • alkyl group e.g. methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, or 2-ethylhexyl
  • a preferable aliphatic group is an alkyl group or an alkenyl group, each of which has from 1 to 30 carbon atoms, more preferably from 1 to 25 carbon atoms, and still more preferably from 1 to 20 carbon atoms, and may have a substituent.
  • Examples of the aromatic group include a benzene ring, a furane ring, a pyrrol ring, a pyridine ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a pyrimidine ring, a pyrazine ring, and condensed rings of these rings, each of which may be substituted.
  • a benzene ring, a pyrrol ring, a pyridine ring, and a thiophene ring are preferred, and a benzene ring and a thiophene ring are more preferred. Especially, a benzene ring is preferred. These rings may be substituted.
  • heterocyclic group examples include a substituted or unsubstituted 3- to 6-membered heterocyclic group, more preferably an unsubstituted 5- or 6-membered heterocyclic group, and still more preferably a 6-membered heterocyclic group (for example, piperidine, morpholine). These groups may have a substituent.
  • m represents 0 or 1. m is preferably 1.
  • the carbon-carbon double bonds in formula (3C) may be any of an E-form or a Z-form.
  • R 8 in formula (3C) represents a sulfur atom or a group represented by formula (5C).
  • the carbon-carbon double bond in formula (5C) may be any of an E-form or a Z-form.
  • R 12C and R 13C in formula (5C) each independently represent a cyano group or an acidic group, and may be the same as or different from each other.
  • the carbon-carbon double bond in formula (5C) may be any of an E-form or a Z-form.
  • R 10C and R 11C each independently represent a cyano group or an acidic group, and may be the same as or different from each other.
  • the carbon-carbon double bond in formula (4C) may be any of an E-form or a Z-form.
  • the group represented by formula (3C) is preferably a group represented by formula (6C).
  • R 9C represents an aliphatic group, an aromatic group or a heterocyclic group (each of which may have an acidic group).
  • B 1C is preferably represented by formula (7C).
  • R 7C represents an aliphatic group, an aromatic group or a heterocyclic group (each of which may have an acidic group).
  • B 1C is preferably a group represented by formula (8C).
  • the substituent include, for example, a halogen atom (e.g. a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom); an alkyl group [which represents a substituted or unsubstituted linear, branched, or cyclic alkyl group, and which includes an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, e.g.
  • a halogen atom e.g. a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom
  • an alkyl group which represents a substituted or unsubstituted linear, branched, or cyclic alkyl group, and which includes an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms, e.g.
  • a cyclohexyl group a cyclopentyl group, or a 4-n-dodecylcyclohexyl group
  • a bicycloalkyl group preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, i.e. a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, e.g. a bicyclo[1.2.2]heptan-2-yl group or a bicyclo[2.2.2]octan-3-yl group), and a tricyclo or higher structure having three or more ring structures; and an alkyl group in substituents described below (e.g.
  • an alkyl group in an alkylthio group represents such an alkyl group of the above concept]; an alkenyl group [which represents a substituted or unsubstituted linear, branched, or cyclic alkenyl group, and which includes an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, e.g. a vinyl group, an allyl group, a prenyl group, a geranyl group, or an oleyl group), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, i.e.
  • a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms e.g. a 2-cyclopenten-1-yl group or a 2-cyclohexen-1-yl group
  • a bicycloalkenyl group which represents a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, i.e. a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond, e.g.
  • a phenyl group a p-tolyl group, a naphthyl group, an m-chlorophenyl group, or an o-hexadecanoylaminophenyl group
  • an aromatic group e.g.
  • a benzene ring a furan ring, a pyrrole ring, a pyridine ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a pyrimidine ring, a pyrazine ring, or rings formed by condensation of the foregoing rings); a heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted 5- or 6-membered aromatic or nonaromatic heterocyclic compound; more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, e.g.
  • a trimethylsilyloxy group or a t-butyldimethylsilyloxy group a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, e.g. a 1-phenyltetrazol-5-oxy group or a 2-tetrahydropyranyloxy group); an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, e.g.
  • a formyloxy group an acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, or a p-methoxyphenylcarbonyloxy group
  • a carbamoyloxy group preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, e.g.
  • a methoxycarbonyloxy group a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group
  • an aryloxycarbonyloxy group preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, e.g.
  • a phenoxycarbonyloxy group a p-methoxyphenoxycarbonyloxy group, or a p-n-hexadecyloxyphenoxycarbonyloxy group
  • an amino group preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, e.g.
  • an amino group preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, e.g.
  • a formylamino group an acetylamino group, a pivaloylamino group, a lauroylamino group, a benzoylamino group, or a 3,4,5-tri-n-octyloxyphenylcarbonylamino group
  • an aminocarbonylamino group preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, e.g.
  • a carbamoylamino group an N,N-dimethylaminocarbonylamino group, an N,N-diethylaminocarbonylamino group, or a morpholinocarbonylamino group
  • an alkoxycarbonylamino group preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, e.g.
  • a methoxycarbonylamino group a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, or an N-methyl-methoxycarbonylamino group
  • an aryloxycarbonylamino group preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, e.g.
  • a phenoxycarbonylamino group a p-chlorophenoxycarbonylamino group, or an m-n-octyloxyphenoxycarbonylamino group
  • a sulfamoylamino group preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, e.g.
  • a sulfamoylamino group an N,N-dimethylaminosulfonylamino group, or an N-n-octylaminosulfonylamino group
  • an alkyl- or aryl-sulfonylamino group preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, e.g.
  • a methylsulfonylamino group a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, or a p-methylphenylsulfonylamino group
  • a mercapto group an alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, e.g.
  • a 2-benzothiazolylthio group or a 1-phenyltetrazol-5-ylthio group a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, e.g.
  • a methylsulfinyl group an ethylsulfinyl group, a phenylsulfinyl group, or a p-methylphenylsulfinyl group
  • an alkyl- or aryl-sulfonyl group preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, e.g.
  • a methylsulfonyl group a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, or a p-methylphenylsulfonyl group
  • an acyl group preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic carbonyl group having 4 to 30 carbon atoms, which is bonded to said carbonyl group through a carbon atom, e.g.
  • an acetyl group a pivaloyl group, a 2-chloroacetyl group, a stearoyl group, a benzoyl group, a p-n-octyloxyphenylcarbonyl group, a 2-pyridylcarbonyl group, or a 2-furylcarbonyl group); an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, e.g.
  • a phenoxycarbonyl group preferably an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, or a p-t-butylphenoxycarbonyl group
  • an alkoxycarbonyl group preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, e.g. a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, or an n-octadecyloxycarbonyl group
  • a carbamoyl group preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, e.g.
  • a carbamoyl group an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N,N-di-n-octylcarbamoyl group, or an N-(methylsulfonyl)carbamoyl group); an aryl- or heterocyclic-azo group (preferably a substituted or unsubstituted aryl azo group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, e.g.
  • a phenylazo group a p-chlorophenylazo group, or a 5-ethylthio-1,3,4-thiadiazol-2-ylazo group
  • an imido group preferably an N-succinimido group or an N-phthalimido group
  • a phosphino group preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, e.g.
  • a dimethylphosphino group a diphenylphosphino group, or a methylphenoxyphosphino group
  • a phosphinyl group preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, e.g. a phosphinyl group, a dioctyloxyphosphinyl group, or a diethoxyphosphinyl group
  • a phosphinyloxy group preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, e.g.
  • a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group a diphenoxyphosphinyloxy group or a dioctyloxyphosphinyloxy group
  • a phosphinylamino group preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, e.g. a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group
  • a silyl group preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, e.g. a trimethylsilyl group, a t-butyldimethylsilyl group, or a phenyldimethylsilyl group).
  • the substituent may be further substituted.
  • examples of the substituent include the substituent W C mentioned above.
  • the dye of the third invention has a maximum absorption wavelength in a solution in a range of preferably from 350 nm to 1,000 nm, more preferably from 370 nm to 700 nm, and especially still more preferably from 390 nm to 650 nm.
  • photoelectric conversion element using any of the dyes of the first invention to the third invention include optical sensors, copying machines, and photoelectrochemical cells.
  • a photoelectrochemical cell is preferred.
  • the dyes of the present invention act as a sensitizing dye.
  • the photoelectric conversion element 10 includes an electrically conductive support 1 ; a photosensitive layer 2 provided on the electrically conductive support 1 , the photosensitive layer having porous semiconductor fine particles to which a dye has been adsorbed; a charge transfer layer 3 ; and a counter electrode 4 .
  • the electrically conductive support 1 having a photosensitive layer 2 provided thereon functions as a working electrode in the photoelectric conversion element 10 .
  • This photoelectric conversion element 10 can be operated as a photoelectrochemical cell (not depicted) by making the element usable in a cell application where the cell is made to work with an external circuit 6 .
  • a light-receiving electrode 5 is an electrode comprising an electrically conductive support 1 ; and a photosensitive layer (semiconductor film layer) 2 coated on the electrically conductive support, the layer containing semiconductor fine particles 22 to which a dye 21 has been adsorbed.
  • a light incident to the photosensitive layer 2 excites the dye.
  • the excited dye has electrons with high energy, and these electrons are transported from the dye 21 to the conduction band of the semiconductor fine particles 22 and further reach the electrically conductive support 1 by diffusion.
  • the molecules of the dye 21 are in an oxide form; however, in a photoelectrochemical cell, the electrons on the electrode return to the oxide of the dye while working in the external circuit, while the light-receiving electrode 5 works as a negative electrode of this cell.
  • the photoelectric conversion element of the present invention makes use of an electrically conductive support 1 .
  • the electrically conductive support a support having electroconductivity per se, such as a metal, or a glass or polymeric material having an electrically conductive layer on the surface can be used. It is preferable that the electrically conductive support is substantially transparent.
  • substantially transparent means that the transmittance of light is 10% or more, preferably 50% or more, particularly preferably 80% or more.
  • a support formed from glass or a polymeric material and coated with an electrically conductive metal oxide can be used.
  • the amount of coating of the conductive metal oxide is preferably 0.1 to 100 g per square meter of the support made of glass or a polymeric material. In the case of using a transparent conductive support, it is preferable that light is incident from the support side.
  • polymeric material examples include tetraacetylcellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyether imide (PEI), cyclic polyolefin, and phenoxy bromide.
  • TAC tetraacetylcellulose
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • SPS syndiotactic polystyrene
  • PPS polyphenylene sulfide
  • PC polycarbonate
  • PAR polyarylate
  • PES polysulfone
  • PET polyester sulfone
  • PEI polyether imide
  • cyclic polyolefin examples include phenoxy bromide.
  • the electrically conductive support may be provided with a light management function at the surface, and for example, the anti-reflective film having a high refractive index film and a low refractive index oxide film alternately laminated as described in JP-A-2003-123859, and the light guide function as described in JP-A-2002-260746 may be mentioned.
  • a metallic support can also be preferably used.
  • examples thereof include titanium, aluminum, copper, nickel, iron, stainless steel and copper. These metals may be alloys. Among these, titanium, aluminum and copper are further preferable; and titanium and aluminum are particularly preferable.
  • the electrically conductive support with a function of blocking ultraviolet light.
  • a method of adopting a fluorescent material that is capable of changing ultraviolet light to visible light as described in JP-A-2001-185242 within the transparent support or on the surface of the transparent support.
  • a method of using an ultraviolet absorbent may also be used. Preferred examples thereof include those described in, for example, JP-A-11-345991, JP-A-2002-25634, JP-A-2003-21769, JP-A-2004-227843, JP-A-2004-349129, JP-A-2002-134178 and JP-A-2003-100358.
  • the conductive support may also be imparted with the functions described in JP-A-11-250944, JP-A-2003-308892 and JP-A-2003-282163.
  • Preferred examples of the electrically conductive film include films of metals (for example, platinum, gold, silver, copper, aluminum, rhodium, and indium), carbon, and electrically conductive metal oxides (for example, indium-tin composite oxide, and fluorine-doped tin oxide).
  • metals for example, platinum, gold, silver, copper, aluminum, rhodium, and indium
  • carbon for example, carbon
  • electrically conductive metal oxides for example, indium-tin composite oxide, and fluorine-doped tin oxide.
  • Preferred examples of the electrically conductive film and the producing method of the same include those described in, for example, JP-A-2003-151355, JP-A-2004-311174, JP-A-2004-311175, JP-A-2004-311176, JP-A-2005-85699, JP-A-2005-85670, JP-A-2005-116391, JP-A-2003-323818, JP-A-2004-165080, and JP-A-2005-141981.
  • the thickness of the conductive film layer is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m.
  • an electrically conductive support having lower surface resistance is preferred.
  • the surface resistance is preferably in the range of 50 ⁇ /cm 2 or less, and more preferably 10 ⁇ /cm 2 or less.
  • the lower limit of the surface resistance is not particularly limited, but the lower limit is usually about 0.1 ⁇ /cm 2 .
  • a collecting electrode may be disposed.
  • Preferred examples of the shape and material of the collecting electrode include those described in, for example, JP-A-11-266028, JP-A-2005-108467, JP-A-2003-203681, JP-A-2004-146425, JP-A-2004-128267, JP-A-2004-164970, JP-A-2004-327226, JP-A-2004-164950, JP-A-2005-78857, JP-A-2005-197176, JP-A-2004-164950, JP-A-2000-285977, JP-A-2002-314108, and JP-A-2003-123858.
  • a gas barrier film and/or an ion diffusion preventing film may be disposed between the support and the transparent conductive film.
  • the gas barrier layer may be any of a resin film (see, for example, JP-A-2000-282163 or JP-A-2005-142086) or an inorganic film (see, for example, JP-A-2005-142086).
  • a transparent electrode and a porous semiconductor electrode photocatalyst-containing layer may also be provided, as described in JP-A-2005-142084 or JP-A-2005-142085.
  • the transparent conductive layer may have a laminate structure, and preferred examples of the production method include the method of laminating FTO on ITO as described in JP-A-2003-323818, as well as the methods described in JP-A-2005-44544, JP-A-2005-142088, JP-A-2005-19205, JP-A-2004-241228 and JP-A-2004-319872.
  • the photosensitive layer 2 in which the dye 2 is adsorbed on the porous semiconductor fine particles 22 is formed on the electrically conductive support 1 .
  • a dispersion liquid of semiconductor fine particles is coated on the above-described electrically conductive support and dried, and then the resultant support is soaked in a solution of the dye of the present invention, thereby making it possible to produce a photosensitive layer.
  • fine particles of chalcogenides of metals for example, oxides, sulfides and selenides
  • fine particles of perovskites may be used with preference.
  • Preferred examples of the chalcogenides of metals include oxides of titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum, cadmium sulfide, and cadmium selenide.
  • Preferred examples of the perovskites include strontium titanate, and calcium titanate. Among these, titanium oxide, zinc oxide, tin oxide, and tungsten oxide are particularly preferred.
  • n-type semiconductors are classified into n-type semiconductors in which the carrier associated with conduction is electron, or p-type semiconductors in which the carrier is a hole. It is preferable to use an n-type semiconductor in the present invention, in view of the conversion efficiency.
  • the n-type semiconductors include an intrinsic semiconductor (or true semiconductor) which does not have an impurity level, and has equal concentrations of the carriers consisting of the conduction band electrons and the valence band holes, as well as an n-type semiconductor having a higher concentration of the electron carrier due to the structural defect originating from impurities.
  • n-type inorganic semiconductors examples include TiO 2 , TiSrO 3 , ZnO, Nb 2 O 3 , SnO 2 , WO 3 , Si, CdS, CdSe, V 2 O 5 , ZnS, ZnSe, SnSe, KTaO 3 , FeS 2 , PbS, InP, GaAs, CuInS 2 , and CuInSe 2 .
  • most preferred examples of the n-type semiconductors include TiO 2 , ZnO, SnO 2 , WO 3 and Nb 2 O 3 .
  • a composite semiconductor material composed of plural kinds of these semiconductors is also used with preference.
  • the particle size of the semiconductor fine particles is such that, for the purpose of maintaining the viscosity of the semiconductor fine particle dispersion liquid high, the average particle size of the primary particles is preferably from 2 nm to 50 nm, and it is more preferable that the semiconductor fine particles are ultrafine particles having an average particle size of the primary particles of from 2 nm to 30 nm. Two or more kinds of fine particles having different particle size distributions may be used in mixture, and in this case, it is preferable that the average size of the smaller particles is 5 nm or less. Also, for the purpose of enhancing the light-capturing rate by scattering the incident light, large particles having an average particle size of more than 50 nm can be added at a low proportion based on the ultrafine particles described above.
  • the content of the large particles is preferably 50% or less, and more preferably 20% or less, by mass of the content of the particles having an average particle size of 50 nm or less.
  • the average particle size of the large particles that are added and mixed for the purpose described above is preferably 100 nm or more, and more preferably 250 nm or more.
  • sol-gel methods described in, for example, Sakka, Sumio, “Science of Sol-Gel Processes”, Agne Shofu Publishing, Inc. (1998) and Technical Information Institute Co., Ltd., “Thin Film Coating Technology Based on Sol-Gel Processes” (1995); and a gel-sol method described in, for example, Sugimoto, Tadao, “Synthesis of Monodisperse Particles and Control of Size and Shape by Gel-Sol Process, a New Synthesis Method”, Materia Japan, Vol. 35, No. 9, pp. 1012-1018 (1996), are preferred.
  • the sol-gel method, the gel-sol method, and the method of hydrolyzing a chloride in an acid hydride salt at high temperature are all preferred, and the sulfuric acid method and chlorine method described in Seino, Manabu, “Titanium Oxide: Material Properties and Application Technologies”, Gihodo Shuppan Co., Ltd. (1997) may also be used.
  • Other preferred examples of the sol-gel method include the method described in Barbe et al., Journal of American Ceramic Society, Vol. 80, No. 12, pp. 3157-3171 (1997), and the method described in Burnside et al., Chemistry of Materials, Vol. 10, No. 9, pp. 2419-2425.
  • examples of the method of producing the semiconductor fine particles include, as preferred methods for producing titania nanoparticles, a method based on flame hydrolysis of titanium tetrachloride (see, for example, JP-T-6-511113 (“JP-T” means searched and published International patent publication)), a method of combusting titanium tetrachloride (see, for example, JP-A-2003-327432), a method of hydrolyzing a stable chalcogenide complex (see, for example, JP-A-2001-85076), hydrolysis of orthotitanic acid (see, for example, JP-A-2004-161589 and JP-A-2004-238213), a method of forming semiconductor fine particles from a soluble portion and an insoluble portion, and then removing by dissolving the soluble portion (see, for example, JP-A-2002-246620), hydrothermal synthesis of an aqueous peroxide solution (see, for example, JP-A-2003-
  • Examples of the crystal structure of titania include structures of anatase type, brookite type and rutile type, and anatase type and brookite type structures are preferred in the present invention.
  • Preferred examples include the structure examples described in JP-A-11-339867, JP-A-2001-43907, and JP-A-2001-43907.
  • Preferred examples of the properties of titanium oxide include the examples described in EP 1 338 563, US 2004/0161380, U.S. Pat. No. 6,075,203, U.S. Pat. No. 6,444,189, U.S. Pat. No. 6,720,202, Chinese Patent 1540772(A), JP-A-2001-283942, and JP-A-2001-212457.
  • titania nanotube/nanowire/nanorod with the titania fine particles.
  • Preferred examples thereof include those described in, for example, JP-A-2003-168495, JP-A-2003-251194, JP-A-2004-175586, JP-A-2004-175587, JP-A-2004-175588, JP-A-2004-311354, JP-A-2004-311355, JP-A-2004-319661, and JP-A-2005-162584.
  • Titania may be doped with a non-metallic element or the like.
  • Preferred examples thereof include those described in, for example, JP-A-2000-235874, JP-A-2003-252624, JP-A-2002-25637, JP-A-2003-187881, JP-A-2003-187882, JP-A-2003-179244, JP-A-2004-87148, JP-A-2004-119279, JP-A-2005-93944, JP-A-2005-64493, JP-A-2003-257507, and JP-A-2003-323920.
  • a binder for improving necking, or a surface additive for preventing reverse electron transfer may also be used.
  • Preferred examples of the additives include ITO or SnO particles (see, for example, JP-A-11-283682 and JP-A-2001-345125), whiskers (see, for example, JP-A-2003-163037), a fibrous graphite/carbon nanotube (see, for example, JP-A-2003-163037), a zinc oxide necking coupler (see, for example, JP-A-2003-273381), fibrous materials such as celluloses (see, for example, JP-A-2003-123861), metals (see, for example, JP-A-2000-285975 and JP-A-2001-35551), organosilicon (see, for example, JP-A-2000-294304), dodecyl benzenesulfonate (see, for example, JP-A-2000-26049
  • titania may be subjected to an acid base treatment or an oxidation reduction treatment before the adsorption of a dye.
  • Preferred examples of the acid base treatment include those described in, for example, JP-A-2000-101106, JP-A-2002-293541, JP-A-2003-297441, JP-A-2003-297442, and JP-A-2004-235240.
  • titania may also be subjected to etching, an oxidation treatment, a hydrogen peroxide treatment, a dehydrogenation treatment, UV-ozone, oxygen plasma or the like, as described in JP-A-8-81222, JP-A-2000-285980, JP-A-2004-158243, JP-A-2004-247104, and the like.
  • Porous semiconductor fine particles-coated layer can be obtained by applying a semiconductor fine particle dispersion liquid in which the content of solids excluding semiconductor fine particles is 10% by mass or less of the total amount of the semiconductor fine particle dispersion liquid, on the electrically conductive support mentioned above, and appropriately heating the coated support.
  • Examples of the method of producing a semiconductor fine particle dispersion liquid include, in addition to the sol-gel method described above, a method of precipitating the semiconductor in the form of fine particles in a solvent upon synthesis and directly using the fine particles; a method of ultrasonicating fine particles, and thereby pulverizing the fine particles into ultrafine particles; a method of mechanically grinding a semiconductor using a mill or a mortar, and pulverizing the ground semiconductor; and the like.
  • a dispersion solvent water and/or various organic solvents can be used.
  • organic solvent examples include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol; ketones such as acetone; esters such as ethyl acetate; dichloromethane, and acetonitrile.
  • alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol
  • ketones such as acetone
  • esters such as ethyl acetate
  • dichloromethane and acetonitrile.
  • a polymer such as polyethylene glycol, hydroxyethylcellulose or carboxymethylcellulose; a surfactant, an acid or a chelating agent may be used in a small amount as a dispersing aid, as necessary. It is preferable that such a dispersing aid is mostly eliminated before the step of forming a film on the electrically conductive support, by a filtration method, a method of using a separating membrane, or a centrifugation method.
  • the semiconductor fine particle dispersion liquid is such that the content of solids excluding semiconductor fine particles is 10% by mass or less based on the total amount of the dispersion liquid.
  • the semiconductor fine particle dispersion liquid may contain a solvent and solids excluding semiconductor fine particles in an amount of 10% by mass or less based on the total amount of the semiconductor fine particle dispersion liquid.
  • the semiconductor fine particle dispersion liquid is substantially composed of semiconductor fine particles and a dispersion solvent.
  • the viscosity of the semiconductor fine particle dispersion liquid is too high, the dispersion liquid undergoes aggregation, and film formation cannot be achieved. On the other hand, if the viscosity of the semiconductor fine particle dispersion liquid is too low, the liquid flows out, and film formation cannot be achieved in some cases.
  • the viscosity of the dispersion liquid is preferably 10 to 300 N ⁇ s/m 2 at 25° C., and more preferably 50 to 200 N ⁇ s/m 2 at 25° C.
  • a roller method, a dipping method or the like can be used as a method involving application.
  • an air knife method, a blade method or the like can be used as a method involving metering.
  • a wire bar method disclosed in JP-B-58-4589 JP-B” means examined Japanese patent publication
  • JP-B means examined Japanese patent publication
  • an extrusion method, a curtain method and a slide hopper method described in U.S. Pat. No. 2,681,294, U.S. Pat. No. 2,761,419 and U.S. Pat. No. 2,761,791, and the like are preferred.
  • a wet printing method include the three major printing methods of relief printing, offset printing and gravure printing, as well as intaglio printing, rubber plate printing, screen printing and the like.
  • a preferable film forming method is selected in accordance with the liquid viscosity or the wet thickness.
  • the semiconductor fine particle dispersion liquid used in the present invention has high viscosity and has viscidity, the fine particle dispersion liquid often has a strong cohesive power, and may not have good affinity to the support upon coating. Under such circumstances, when surface cleaning and hydrophilization are carried out through a UV-ozone treatment, the affinity between the applied semiconductor fine particle dispersion liquid and the surface of the electrically conductive support increases, and thus it becomes easier to apply the semiconductor fine particle dispersion liquid.
  • the thickness of the entire semiconductor fine particle layer is preferably 0.1 to 100 ⁇ m, more preferably 1 to 30 ⁇ m, and even more preferably 2 to 25 ⁇ m.
  • the amount of the coated semiconductor fine particles per square meter of the support is preferably 0.5 to 400 g, and more preferably 5 to 100 g.
  • the applied layer of semiconductor fine particles is subjected to a heating treatment, for the purpose of reinforcing the electronic contact between semiconductor fine particles and enhancing the adhesiveness of the semiconductor fine particles to the support, and also in order to dry the applied semiconductor fine particle dispersion liquid.
  • the porous semiconductor fine particle layer can be formed by this heating treatment.
  • light energy can also be used in addition to the heating treatment.
  • the surface may be activated by providing the light that is absorbed by the semiconductor fine particles, such as ultraviolet light, or only the surface of the semiconductor fine particles can be activated with a laser light or the like.
  • the semiconductor fine particles are irradiated with a light that is absorbed by the fine particles, the impurities adsorbed to the particle surfaces are decomposed as a result of activation of the particle surfaces, and a state preferable for the purpose described above can be attained.
  • the heating is carried out at a temperature of preferably from 100° C. to 250° C., more preferably from 100° C.
  • the semiconductor fine particles are irradiated with the light that is absorbed by the fine particles.
  • the impurities incorporated in the fine particle layer can be washed away by photodecomposition, and the physical bonding between the fine particles can be reinforced.
  • Examples of the method of applying pressure include the methods described in JP-T-2003-500857, JP-A-2002-93475, JP-A-2003-282160 and JP-A-2004-214129.
  • Examples of the light irradiation method include the methods described in JP-A-2001-357896, JP-A-11-219734, JP-A-2004-314313, JP-A-2005-142446, and JP-A-2001-247314.
  • Examples of the methods utilizing plasma, microwaves or electric current include the methods described in JP-A-2002-353453, JP-A-2003-308893, JP-A-2004-265662, JP-A-2004-327369, JP-A-2004-342319, JP-A-2005-116415, JP-A-2005-139498, and JP-A-2004-273770.
  • Examples of the chemical treatment include the methods described in JP-A-2001-357896, JP-A-2002-280327, JP-A-2003-281947, JP-T-2005-520314 and JP-A-2003-297442.
  • the method of coating the semiconductor fine particles on the electrically conductive support is included in the (1) wet methods, such as a method of applying a semiconductor fine particle dispersion liquid on an electrically conductive support; and a method of applying a precursor of the semiconductor fine particles on an electrically conductive support, hydrolyzing the precursor under the action of the moisture in air, and thereby obtaining a semiconductor fine particle film, as described in Japanese Patent No. 2664194.
  • examples of the method of preparing a dispersion liquid of semiconductor fine particles include, in addition to the methods described above, a method of pulverizing fine particles in a mortar; a method of dispersing fine particles while pulverizing the particles using a mill; a method of precipitating fine particles in a solvent upon synthesizing a semiconductor, and directly using the precipitates; and the like.
  • Preferred examples thereof include those described in, for example, JP-A-11-144772, JP-A-2005-100792, EP 1 300 897 A1, JP-A-2002-324591, JP-A-2002-145615, JP-A-2003-176130, and JP-A-2004-79610.
  • the dispersion medium for the coating liquid used in the (1) wet methods may be water, or various organic solvents (for example, methanol, ethanol, t-butanol, dichloromethane, acetone, acetonitrile and ethyl acetate). Preferred examples thereof include those described in, for example, JP-T-6-511113, CN Patent No.
  • JP-A-11-11912 JP-A-2000-294814, JP-A-2000-319018, JP-A-2000-319018, JP-A-2000-319018, JP-A-2002-145614, JP-A-2002-75477, JP-A-2004-193321, WO 02/067357, JP-A-2004-207205, JP-A-2004-111348, JP-A-2004-186144, JP-A-2003-282162, JP-A-2005-142011, JP-A-2005-174695, JP-A-2005-85500, JP-A-11-343118, JP-A-11-354169, JP-A-2000-106222, JP-A-2003-246621, JP-A-2003-51345, JP-A-2004-158551, JP-A-2001-358348, and JP-A-2003-217693.
  • a polymer Upon dispersing the semiconductor fine particles, a
  • Preferred examples of the (2) dry methods include the methods described in JP-A-2000-231943, JP-A-2002-170602, JP-A-2001-345124, JP-A-2003-197280, JP-A-2003-123854, JP-A-2003-123852, JP-A-2003-123853, JP-A-2005-39013, JP-A-2004-39286, and JP-A-2005-104760.
  • Preferred examples of the (3) other methods include the methods described in JP-A-2002-134435, US 2004/0123896, JP-A-2004-327265, JP-A-342397, JP-T-2003-500857, JP-A-2005-85491, JP-A-2003-98977, JP-A-2002-299665, JP-A-2003-243053, JP-A-2004-253331, JP-A-11-310898, JP-A-2003-257507, JP-A-2003-323920, US 2004/0084080, US 2004/0121068, JP-A-2004-319873, JP-A-10-112337, JP-A-11-6098, JP-A-2000-178791, JP-A-2000-178792, JP-A-2004-103420, and JP-A-2003-301283.
  • the semiconductor fine particles it is preferable for the semiconductor fine particles to have a large surface area, so that a large amount of dye can adsorb to the surface.
  • the surface area is preferably 10 times or more, and more preferably 100 times or more, relative to the projected surface area.
  • the upper limit of this value is not particularly limited, but the upper limit is usually about 5000 times.
  • Preferred examples of the structure of the semiconductor fine particles include the structures disclosed in JP-A-2001-93591, JP-A-2001-257012, JP-A-2001-196106, JP-A-2001-273936, and EP No. 1207572 A1.
  • the thickness of the semiconductor fine particle layer increases, the amount of dye that can be supported per unit area increases, and therefore, the light absorption efficiency is increased. However, since the diffusion distance of generated electrons increases along, the loss due to charge recombination is also increased.
  • a preferred thickness of the semiconductor fine particle layer may vary with the utility of the element, the thickness is typically 0.1 to 100 ⁇ m.
  • the thickness of the semiconductor fine particle layer is preferably 1 to 50 ⁇ m, and more preferably 3 to 30 ⁇ m.
  • the semiconductor fine particles may be calcined after being applied on the support, at a temperature of 100 to 800° C. for 10 minutes to 10 hours, so as to bring about cohesion of the particles. When a glass support is used, the film forming temperature is preferably 400 to 600° C.
  • the method of forming a film in this case may be any of (1) a wet method, (2) a dry method, and (3) an electrophoresis method (including an electrocrystallization method); preferably (1) a wet method or (2) a dry method; and further preferably (1) a wet method.
  • the wet method is a method of forming a film on a plastic film by applying a semiconductor layer or a precursor thereof in a wet manner or the like, and further activating the semiconductor layer.
  • the wet method include the method of heating a mixture of a semiconductor and an electrically conductive compound at low temperature as described in JP-A-10-290018; a method of utilizing a precursor (examples of the precursor include (NH 4 ) 2 TiF 6 described in JP-A-2001-110462; titanium peroxide described in JP-A-2001-247314; and a metal alkoxide, a metal complex and an organic acid metal salt described in JP-A-11-219734); a method of applying a slurry additionally containing a metal organic oxide (alkoxide or the like), and forming a semiconductor film by a heating treatment, a light treatment or the like, as described in JP-T-2005-520314; and a method of characterizing the pH of the slurry additionally containing an inorgan
  • binder examples include the celluloses described in JP-A-2003-109678 or JP-A-2003-123861; the fluoropolymers described in JP-A-2003-272722; the crosslinked rubber described in JP-A-2004-47261; the polybutyl titanate described in JP-T-2005-516365; and the carboxymethylcellulose described in JP-A-2005-135798.
  • Examples of the technique related to the formation of a layer of a semiconductor or a precursor thereof include a method of hydrophilizing the layer by a physical method using corona discharge, plasma, UV or the like; a chemical treatment based on an alkali (see, for example, JP-A-2004-119120) or on polyethylene dioxythiophene and polystyrenesulfonic acid (see, for example, JP-A-2005-169228) or the like; formation of an intermediate film for bonding of polyaniline or the like as described in JP-A-2003-297443.
  • Examples of the dry method include deposition, sputtering, an aerosol deposition method, and the like. Preferred examples thereof include methods described in, for example, JP-A-2005-39013, JP-A-2004-074609, Japanese Patent No. 3265481, JP-A-2003-100359, and JP-A-2004-39286.
  • electrophoresis method and the electrocrystallization method described in JP-A-2002-100146 and JP-A-2004-311354 may also be used.
  • a method of first preparing a coating film on a heat resistant base, and then transferring the film to a film made of plastic or the like may be used.
  • a method of transferring a layer through EVA as described in JP-A-2002-184475; a method of forming a semiconductor layer and a conductive layer on a sacrificing base containing an inorganic salt that can be removed by ultraviolet rays or a water-based solvent, subsequently transferring the layers to an organic base, and removing the sacrificing base as described in JP-A-2003-98977; and the like may be used.
  • the amount of coating of the semiconductor fine particles per square meter of the support is preferably 0.5 to 500 g, and more preferably 5 to 100 g.
  • a photosensitive layer can be obtained by adsorbing the dye of the present invention to a porous semiconductor fine particle layer which has been obtained by applying the semiconductor fine particle dispersion liquid described above, on the electrically conductive support described above, and heating the semiconductor fine particle layer.
  • the photosensitive layer is designed according to the purpose, and may have a single layer constitution or a multilayer constitution. Furthermore, the dye in the photosensitive layer may be of one kind or may be a mixture of plural kinds, but the above-described dye of the present invention is used for at least one kind of the plural kinds.
  • the photosensitive layer of the photoelectric conversion element produced by the method of the present invention contains semiconductor fine particles having this dye adsorbed thereto, and has high sensitivity. When the photoelectric conversion element is used for a photoelectrochemical cell, a high conversion efficiency can be obtained.
  • the dye (dye compound) of the present invention can be synthesized by, for example, methods described or cited in F. M. Harmer, “Heterocyclic Compounds—Cyanine Dyes and Related Compounds”, John Wiley & Sons, New York and London, 1994, or methods similar thereto.
  • any solvent capable of dissolving the dye of the present invention can be used without any particular limitation.
  • ethanol methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone or n-butanol can be used.
  • ethanol and toluene can be preferably used.
  • the dye solution for dye adsorption formed from a solvent and the dye of the present invention may be heated if necessary, at 50° C. to 100° C. Adsorption of the dye may be carried out before or after the process of applying the semiconductor fine particles. Adsorption of the dye may also be conducted by simultaneously applying the semiconductor fine particles and the dye. Any unadsorbed dye is removed by washing. In the case of performing calcination of the coating film, it is preferable to carry out the adsorption of the dye after calcination. After calcination has been performed, it is particularly preferable to perform the adsorption of the dye rapidly before water adsorbs to the surface of the coating film.
  • the dye to be adsorbed may be composed of a single kind, or a mixture of plural kinds of dyes may also be used.
  • a mixture two or more kinds of dyes of the present invention may be mixed, or the dye of the present invention may be mixed with a complex dye described in U.S. Pat. No. 4,927,721, U.S. Pat. No. 4,684,537, U.S. Pat. No. 5,084,365, U.S. Pat. No. 5,350,644, U.S. Pat. No. 5,463,057, U.S. Pat. No. 5,525,440, and JP-A-7-249790.
  • the dyes are selected so that the wavelength region for photoelectric conversion can be made as broad as possible when the dyes are mixed.
  • the overall amount of use of the dye is preferably 0.01 to 100 millimoles, more preferably 0.1 to 50 millimoles, and particularly preferably 0.1 to 10 millimoles, per square meter of the support.
  • the amount of use of the dye of the present invention is preferably adjusted to 5% by mole or more.
  • the amount of the dye adsorbed to the semiconductor fine particles is preferably 0.001 to 1 millimole, and more preferably 0.1 to 0.5 millimoles, based on 1 g of the semiconductor fine particles.
  • the sensitization effect for the semiconductor can be sufficiently obtained.
  • the amount of the dye is too smaller, the sensitization effect is insufficient, and if the amount of the dye is excessive, the portion of the dye that is not attached to the semiconductor is suspended, and causes a decrease in the sensitization effect.
  • a colorless compound may be co-adsorbed.
  • hydrophobic compound that is co-adsorbed include steroid compounds having a carboxyl group (for example, cholic acid and pivaloyl acid).
  • the surface of the semiconductor fine particles may be treated using amines.
  • amines include 4-tert-butylpyridine, and polyvinylpyridine. These may be used directly when the compounds are liquids, or may be used in a state of being dissolved in an organic solvent.
  • the charge transfer layer is a layer having a function of supplementing electrons to an oxidant of the dye, and is provided between the light-receiving electrode and the counter electrode.
  • Representative examples of the material forming the charge transfer layer include a liquid prepared by dissolving a redox pair in an organic solvent, a so-called gel electrolyte obtained by impregnating a polymer matrix with a liquid prepared by dissolving a redox pair in an organic solvent, and a molten salt containing a redox pair.
  • Examples of the redox pair include a combination of iodine and an iodide (for example, lithium iodide, tetrabutylammonium iodide, or tetrapropylammonium iodide), a combination of an alkylviologen (for example, methylviologen chloride, hexylviologen bromide, or benzylviologen tetrafluoroborate) and a reductant thereof, a combination of a polyhydroxybenzene (for example, hydroquinone or naphthohydroquinone) and an oxidant thereof, and a combination of a divalent iron complex and a trivalent iron complex (for example, potassium ferricyanide and potassium ferrocyanide).
  • an alkylviologen for example, methylviologen chloride, hexylviologen bromide, or benzylviologen tetrafluoroborate
  • a combination of a polyhydroxybenzene for example,
  • a combination of iodine and an iodide is preferred.
  • the organic solvent that dissolves these materials include aprotic polar solvents (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethylsulfoxide, sulfolane, 1,3-dimethylimidazolinone, and 3-methyloxazolidinone); the water-containing electrolyte liquid described in JP-A-2002-110262; and the electrolyte solvents described in JP-A-2000-36332, JP-A-2000-243134 and WO 00/54361.
  • preferred organic solvents are acetonitrile, methoxypropionitrile, propylene carbonate and ⁇ -butyrolactone.
  • additives that are added to the electrolyte include 4-tert-butylpyridine mentioned above, as well as the pyridine and pyridine-based compounds described in JP-A-2003-331986; the aminopyridine-based compounds described in JP-A-2004-47229, JP-A-2004-171821 and the like; the benzimidazole-based compounds described in JP-A-2004-273272; the aminotriazole-based compounds and aminothiazole-based compounds described in JP-A-2005-38711; the imidazole-based compounds described in JP-A-2005-108663; quinoline-based compounds (see, for example, JP-A-2005-135782); aminotriazine-based compounds (see, for example, JP-A-2005-183166); urea derivatives (see, for example, JP-A-2003-168493); amide compounds (see, for example, JP-A-2004-103404); pyrimidine-based compounds (see, for example, J
  • a method of controlling the water content of the electrolyte liquid in order to enhance the efficiency.
  • Preferred examples of the method of controlling the water content include a method of controlling the concentration (see, for example, JP-A-2000-323189 and JP-A-2001-76774), and a method of adding a dehydrating agent (see, for example, JP-A-2002-237335 and JP-A-2002-237335).
  • a clathrate compound of iodine with cyclodextrin may be used as described in JP-A-2004-235011.
  • a method of supplying moisture on a steady basis may be used as described in JP-A-2003-25709.
  • a cyclic amidine may be used as described in Japanese Patent No.
  • an oxidation inhibitor see, for example, JP-A-2004-39292
  • a hydrolysis inhibitor see, for example, JP-A-2004-111276
  • a decomposition inhibitor see, for example, JP-A-2004-111277
  • zinc iodide see, for example, JP-A-2004-152613
  • a molten salt may also be used as the electrolyte, and preferred examples of the molten salt include an ionic liquid containing an imidazolium or triazolium type cation (see, for example, JP-T-9-507334, JP-A-8-259543, JP-A-2003-31270, JP-A-2005-112733, JP-A-2005-116367, JP-A-2005-112733, JP-A-2003-68374, JP-A-2003-92153, JP-A-2004-241378, JP-A-2005-85587 and JP-A-2004-87387); an oxazolium-based salt (see, for example, JP-A-2000-53662); a pyridinium-based salt (see, for example, JP-A-2000-58891, JP-A-2001-23705, JP-A-2001-167630, JP-A-2001-256828, and JP-A-2001-266962
  • additives may be added these molten salts, and preferred examples of the additives include those described in JP-A-2001-67931, JP-A-2001-160427, JP-A-2002-289267, JP-A-2002-289268, JP-A-2000-90991, JP-A-2000-100485, JP-A-2001-283943, and the like.
  • the molten salt may have a substituent having liquid crystalline properties.
  • the quaternary ammonium salt-based molten salt described in JP-A-2005-104845, JP-A-2005-104846, JP-A-2005-179254 and the like may also be used.
  • Molten salts other than those described above include, for example, the molten salts described in JP-A-2005-139100 and JP-A-2005-145927, as well as a molten salt to which fluidity at room temperature has been imparted by mixing lithium iodide and at least one kind of other lithium salt (for example, lithium acetate or lithium perchlorate) with polyethylene oxide.
  • the amount of addition of the polymer in this case is 1 to 50% by mass.
  • the electrolyte liquid may contain ⁇ -butyrolactone, and this ⁇ -butyrolactone increases the diffusion efficiency of iodide ions, and thereby, the conversion efficiency is enhanced.
  • the electrolyte may be quasi-solidified by adding a gelling agent to an electrolyte liquid formed from an electrolyte and a solvent, and gelling the electrolyte liquid thereby.
  • the gelling agent include an organic compound having a molecular weight of 1000 or less (see, for example, JP-A-11-185836, JP-A-2000-36608 and JP-A-2000-58140); an Si-containing compound having a molecular weight in the range of 500 to 5000 (see, for example, JP-A-2003-203520); an organic salt obtained from a particular acidic compound and a particular basic compound (see, for example, JP-A-2003-203520); a sorbitol derivative (see, for example, JP-A-2003-346928); and polyvinylpyridine (see, for example, JP-A-2004-227920 and JP-A-2005-93370).
  • a method of confining a matrix polymer, a crosslinked type polymer compound or monomer, a crosslinking agent, an electrolyte and a solvent, in a polymer may be used.
  • the matrix polymer include a polymer having a nitrogen-containing heterocyclic ring in a repeating unit in the main chain or in a side chain, and a crosslinked structure formed by reacting the polymer with an electrophilic compound (see, for example, JP-A-11-12691 and JP-A-2000-86724); a polymer having a triazine structure and a polymer having a ureide structure (see, for example, JP-A-2000-251532); a polymer containing a liquid crystalline compound (see, for example, JP-A-2000-319260 and JP-A-2002-246066), a polymer having an ether bond (see, for example, JP-A-2000-150006, JP-A-2002-63813, JP-A-2001-338700, and JP-A-2002-75480); a polyvinylidene fluoride-based polymer (see, for example, JP-A-2003-303628); a methacrylate
  • An alkali-swellable polymer (see, for example, JP-A-2002-175482), a polymer having a component capable of forming a charge transfer complex with a cation moiety and iodine within one polymer molecule (see, for example, JP-A-2005-63791), or the like may be added to those matrix polymers.
  • a system containing, as a matrix polymer, a crosslinked polymer formed by reacting a bifunctional or higher-functional isocyanate as one component with a functional group such as a hydroxyl group, an amino group or a carboxyl group, may also be used. Examples of this system are described in JP-A-2000-228234, JP-A-2002-184478, JP-A-2002-289271 and JP-A-2003-303630.
  • a crosslinked polymer based on a hydrosilyl group and a double-bonded compound see, for example, JP-A-2003-59548
  • a crosslinking method involving reacting polysulfonic acid, polycarboxylic acid or the like with a divalent or higher-valent metal ion compound see, for example, JP-A-2003-86258, and the like may also be used.
  • Examples of the solvent that can be used with preference in combination with the quasi-solid electrolyte described above include particular phosphates (see, for example, JP-A-2000-100486 and JP-A-2003-16833); a mixed solvent containing ethylene carbonate (see, for example, JP-A-2004-87202); a solvent having a particular relative permittivity (see, for example, JP-A-2004-335366); and the solvents described in JP-A-2003-16833 and JP-A-2003-264011.
  • a liquid electrolyte solution may be retained in a solid electrolyte membrane or in pores, and preferred examples of the method include the usage of an electrically conductive polymer membrane (JP-A-11-339866), a fibrous solid (JP-A-2000-357544), and a fabric-like solid such as filter (JP-A-2001-345125). It is also acceptable to use the particular combination of a gel electrolyte and an electroconductive resin counter electrode described in JP-A-2003-157914.
  • a solid charge transport system such as a p-type semiconductor or a hole transporting material may also be used instead of the liquid electrolytes and quasi-solid electrolytes described above.
  • Preferred examples of the p-type semiconductor include CuI (see, for example, JP-A-2001-156314, JP-A-2001-185743, JP-A-2001-185743, JP-A-2001-230434, JP-A-2003-273381, JP-A-2003-234485, JP-A-2003-243681, and JP-A-2003-234486), CuSCN and p-SbAl (see, for example, JP-A-2003-258284).
  • Preferred examples of the producing method of the hole transporting material include those described in JP-A-2003-331938, JP-A-2001-168359, JP-A-2001-196612, JP-A-2001-257370, JP-A-2002-246623, JP-A-2002-246624, and JP-A-2003-289151.
  • a photoelectrochemical cell having high conversion efficiency can be obtained by using a laminate in which a hole transporter is provided adjacent to a photosensitive layer of the semiconductor fine particles having the dye of the present invention adsorbed thereto.
  • the hole transporter is not particularly limited, but an organic hole transporting material can be used.
  • Preferred examples of the hole transporter include electrically conductive polymers such as polythiophene (see, for example, JP-A-2000-106223 and JP-A-2003-364304), polyaniline (see, for example, JP-A-2003-264304), polypyrrole (see, for example, JP-A-2000-106224 and JP-A-2003-264304), and polysilane (see, for example, JP-A-2001-53555 and JP-A-2001-203377); a spiro compound in which two rings share a central element adopting a tetrahedral structure, such as C and Si (see, for example, JP-T-11-513522 and JP-T-2001-525108); aromatic amine derivatives such as triarylamine (see, for example, JP-A-11-144773, JP-A-11-339868, JP-A-2003-123856, JP-A-2003-197942 and JP-A-2004-356281
  • the redox pair serves as a carrier for electrons, and thus is required at a certain concentration.
  • a preferred overall concentration is 0.01 moles/liter or more, more preferably 0.1 moles/liter or more, and particularly preferably 0.3 moles/liter or more.
  • the upper limit of the concentration is not particularly limited, but is usually about 5 moles/liter.
  • the counter electrode is an electrode working as a positive electrode in the photoelectrochemical cell.
  • the counter electrode usually has the same meaning as the electrically conductive support described above, but in a construction which is likely to maintain a sufficient strength, a support is not necessarily required. However, a construction having a support is advantageous in terms of sealability.
  • the material for the counter electrode include platinum, carbon, and electrically conductive polymers.
  • Preferred examples include platinum (see, for example, JP-A-2001-102102), carbon (see, for example, JP-A-2002-298936, JP-A-2003-297446, JP-A-2004-127849, JP-A-2004-152747, JP-A-2004-165015, JP-A-2004-111216, JP-A-2004-241228, and JP-A-2004-319872), and electrically conductive polymers (see, for example, JP-A-2003-317814, JP-A-2004-319131, and JP-A-2005-116301). Materials described in JP-A-2001-43908, JP-A-2003-142168, JP-A-2004-127849 and JP-A-2004-152747 may also be used.
  • a preferred structure of the counter electrode is a structure having a high charge collecting effect.
  • Preferred examples thereof include those described in JP-A-10-505192, JP-A-2004-296669, JP-A-2005-11609, JP-A-2005-141996, JP-A-2005-142090, JP-A-2005-158470, JP-A-2000-348784, JP-A-2005-158379, JP-A-2000-294305, JP-A-2001-243995, JP-A-2004-241228, JP-A-2004-296203, JP-A-2004-319872, and JP-A-2005-197097.
  • a composite electrode of titanium oxide and tin oxide (TiO 2 /SnO 2 ) or the like may be used.
  • mixed electrodes of titania include those described in JP-A-2000-113913, JP-A-2004-95387, JP-A-2001-155791, JP-A-2003-272723, JP-A-05-504023, JP-A-2000-114563, JP-A-2002-75476, JP-A-2002-8741, CN 1350334(A), JP-A-2003-272724, JP-A-2003-308891, JP-A-2005-174934, JP-A-2001-358348, JP-A-2003-123862, JP-A-2004-103420, JP-A-2005-39013 and JP-A-2003-317815.
  • Examples of mixed electrodes of materials other than titania include those described in JP-A-2001-185243, JP-A-2003-282164, JP-A-2003-289151, JP-A-2003-321299, JP-A-2002-93471, JP-A-2002-141115, JP-A-2002-184476, JP-A-2002-356400, JP-A-2002-246623, JP-A-2002-246624, JP-A-2002-261303, JP-A-2003-243053, JP-A-2004-6235, JP-A-2003-323920, JP-A-2004-277197, JP-A-2004-210605, JP-A-2005-135798, JP-A-2005-135799, JP-A-2001-196105, JP-A-2002-100418, JP-A-2002-100419, JP-A-2002-280084, JP-A-2003-272724, JP-A-2004-124124
  • the light-receiving electrode may be a tandem type electrode so as to increase the utility ratio of the incident light, or the like.
  • Preferred examples of the tandem type construction include those described in JP-A-2002-90989, JP-A-2002-222971, JP-A-2003-168496, JP-A-2003-249275, JP-A-2005-166313, JP-A-11-273753, JP-A-2002-167808, JP-A-2005-129259, JP-A-2002-231324, JP-A-2005-158620, JP-A-2005-158621, JP-A-2005-191137 and JP-A-2003-333757.
  • the light-receiving electrode may be provided with the photo management function by which light scattering and reflection are efficiently achieved inside the light-receiving electrode layer.
  • Preferred examples thereof include those described in JP-A-2002-93476, JP-A-2004-296373, JP-A-2002-352868, JP-A-2003-142170, JP-A-2003-59549, JP-A-2002-289274, JP-A-2002-222968, JP-A-2003-217688, JP-A-2004-172110, JP-A-2003-303629, JP-A-2004-343071, JP-A-2005-116302, JP-A-9-259943, JP-A-10-255863, JP-A-2003-142171, JP-A-2002-110261, and JP-A-2004-311197.
  • a short circuit preventing layer between the electrically conductive support and the porous semiconductor fine particle layer, so as to prevent reverse current due to a direct contact between the electrolyte liquid and the electrode.
  • Preferred examples thereof include those described in JP-T-6-507999, JP-A-6-51113, JP-A-2000-178792, JP-A-11-312541, JP-A-2000-285974, JP-A-2000-285979, JP-A-2001-143771, JP-A-2001-156314, JP-A-2001-307785, JP-A-2002-151168, JP-A-2002-75471, JP-A-2003-163359, JP-A-2003-163360, JP-A-2003-123856, WO 03/038909, JP-A-2002-289270, JP-A-2002-319439, JP-A-2003-297443, JP-A-2004-87622, JP-A-2003
  • a spacer or a separator so as to prevent the contact between the light-receiving electrode and the counter electrode.
  • Preferred examples thereof include those described in JP-A-2001-283941, JP-A-2003-187883, JP-A-2000-294306, JP-A-2002-175844, JP-A-2002-367686, and JP-A-2004-253333.
  • D-1 and D-3 as the dye of the first invention were prepared according to the production method of the first invention.
  • the exemplified dye D-1 was prepared according to the method shown in the following scheme 1.
  • the exemplified dye D-3 was prepared in the same manner as in the above-described exemplified dye D-1, according to the method shown in the following scheme 2.
  • the exemplified dyes D-2 and D-4 to D-16 were synthesized in the same manner as in Synthesis Examples 1-1 and 2-1.
  • the exemplified dye D-1 was prepared according to the method shown in the following scheme 3.
  • A-1, A-4, A-5, A-26, A-3, A-2, A-46, A-9, A-10, A-16, A-29, A-47, A-48, A-50, A-51, A-52 and A-53 were prepared as the dye of the second invention.
  • the exemplified dye A-1 was prepared according to the method shown below.
  • the exemplified dye A-4 was prepared according to the method shown below.
  • the exemplified dye A-5 was prepared by making the intermediate B-1 prepared separately react with A-1d.
  • the exemplified dye A-8 was prepared according to the method shown below.
  • the exemplified dye A-26 was prepared according to the method shown below.
  • the exemplified dye A-3 was prepared according to the method shown below.
  • the exemplified dye A-2 was prepared by making Intermediate B-2 prepared separately react with A-2d.
  • the exemplified dye A-46 was prepared according to the method shown below.
  • the exemplified dye A-17 was prepared according to the method shown below.
  • the exemplified dye A-9 was prepared according to the method shown below.
  • the exemplified dye A-10 was prepared according to the method shown below.
  • the exemplified dye A-16 was prepared according to the method shown below.
  • the exemplified dye A-29 was prepared according to the method shown below.
  • the exemplified dye A-47 was prepared according to the method shown below.
  • the exemplified dye A-48 was prepared by using the intermediate B-3 prepared separately.
  • the intermediate B-3 was prepared according to the method shown below.
  • the exemplified dye A-48 was prepared by using the thus-obtained intermediate B-3.
  • the exemplified dye A-49 was prepared by using Intermediate B-2 prepared separately.
  • the exemplified dye A-50 was prepared by using Intermediate B-2 prepared separately.
  • the exemplified dye A-51 was prepared by using Intermediate B-2 prepared separately.
  • the reaction liquid was left to cool to room temperature, and then water was added to the reaction liquid and precipitated crystals were collected by filtration.
  • the crystals thus obtained were purified by recrystallization, and thus 0.7 g of A-51 was obtained.
  • the exemplified dye A-52 was prepared according to the method shown below.
  • the exemplified dye A-53 was prepared by using
  • CA-1 and CA-4 were prepared as the dyes of the third invention.
  • the exemplified dye CA-1 was prepared according to the method shown in the following scheme.
  • reaction solution was added to a 14 wt % aqueous solution of sodium acetate, and stirred at room temperature for 30 minutes.
  • the resultant solution was extracted twice with ethyl acetate.
  • the ethyl acetate extracts were mixed together, and washed with water.
  • magnesium sulfate a solvent was distilled away under reduced pressure to obtain a crude product.
  • each of azepine derivatives in which two of the hexyl-substituted thiophene rings represented by A-4-b are linked together, azepine derivatives in which three of the hexyl-substituted thiophene rings represented by A-4-d are linked together, and azepine derivatives in which four of the hexyl-substituted thiophene rings represented by A-4-f are linked together, can be synthesized.
  • a photoelectric conversion element such as shown in FIG. 1 was produced as follows.
  • a film of tin oxide doped with fluorine was formed by sputtering as a transparent conductive film, and this film was scribed with a laser to partition the transparent conductive film into two parts.
  • anatase type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) was incorporated into 100 ml of a mixed solvent composed of water and acetonitrile at a volume ratio of 4:1, and the mixture was uniformly dispersed and mixed using a mixing conditioner of rotation/revolution combination type. Thus, a dispersion liquid of semiconductor fine particles was obtained. This dispersion liquid was applied on the transparent conductive film and heated, and thus a light-receiving electrode was produced.
  • a dispersion liquid containing silica particles and rutile type titanium oxide at a ratio of 40:60 (mass ratio) was similarly prepared, and this dispersion liquid was applied on the light-receiving electrode described above and heated. Thus, an insulating porous body was formed. Subsequently, a carbon electrode was formed as a counter electrode.
  • the glass substrate having the insulating porous body formed thereon was immersed for 48 hours in an ethanol solution of each of the sensitizing dyes indicated in the following Table 1-1 (3 ⁇ 10 ⁇ 4 mol/L).
  • the glass dyed with the sensitizing dye was immersed for 30 minutes in a 10% ethanol solution of 4-tert-butylpyridine, and then the glass was washed with ethanol and naturally dried.
  • the photosensitive layer thus obtained had a thickness of 10 ⁇ m, and the application amount of the semiconductor fine particles was 20 g/m 2 .
  • a methoxypropionitrile solution of dimethylpropylimidazolium iodide (0.5 mol/L) and iodine (0.1 mol/L) was used.
  • the maximum absorption wavelength of the sensitizing dye used was measured. The results are presented in Table 1-1. The measurement was carried out using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corp.), and an ethanol solution was used.
  • Pseudo-sunlight which did not include ultraviolet radiation was generated by passing the light of a 500-W xenon lamp (manufactured by Ushio, Inc.) through an AM1.5G filter (manufactured by Oriel Instruments Corp.) and a sharp cutoff filter (Kenko L-42, trade name). The intensity of this light was 89 mW/cm 2 .
  • the produced photoelectric conversion element was irradiated with this light, and the electricity thus generated was measured with a current-voltage measuring device (Keithley-238 type, trade name). The results of measuring the conversion efficiencies of the photoelectrochemical cells thus determined are presented in the following Table 1-1.
  • sensitizing dye A For Sample No. 13, the following sensitizing dye A described in JP-A-11-214730 was used. In the tables of the following Examples, all of the dyes referred to as sensitizing dye A are dyes represented by the following formula.
  • Electrochemical cells produced by using the dyes of the present invention exhibited conversion efficiency values as high as 5% or more, particularly when compounds D-1 to D-3 and D-7 to D-9 were used as the dye, as shown in Table 1-1. Even when other dyes of the present invention were used, the conversion efficiency was at a practically usable level of equal to or more than 2% and less than 5%. Even in the case where the compound I-1 was contained in D-1 in an amount of 0.2 ppm (Sample No. 17), the effect was negligible, and the conversion efficiency was 5% or more. Also, in the case where Pd attributable to the palladium complex used in the synthesis of D-1 was incorporated in an amount of 0.1 ppm (Sample No. 18), the effect was negligible, and the conversion efficiency was 5% or more.
  • Comparative Example of Sample No. 17 had a conversion efficiency of equal to or more than 0.5% and less than 2%, and was unsatisfactory to be used in electrochemical cells.
  • Example 1-1 An evaluation was performed in the same manner as in Example 1-1, using the dye of the second embodiment of the present invention that was prepared as described above. The results were shown in Table 1-2.
  • Electrochemical cells produced by using the dye of the second embodiment exhibited conversion efficiency values as high as 5% or more, particularly when compounds A1 to A7, A12 to A15, A-18, A-19, A-21, A-24, A-26 to A-31, A-33 to A-35, A-41, A-43, A-44, A-50, A-52 and A-53 were used as the dye, as shown in Table 1-2. Even when other dyes of the present invention were used, the conversion efficiency was at a practically usable level of equal to or more than 2% and less than 5%.
  • Comparative Example of Sample No. 54 had a conversion efficiency of equal to or more than 0.5% and less than 2%, and was unsatisfactory to be used in electrochemical cells.
  • Example 1-1 An evaluation was performed in the same manner as in Example 1-1, using the dye of the third embodiment of the present invention prepared as described above. The results are presented in Tables 1-3 to 1-5.
  • Electrochemical cells produced by using the dyes of the present invention exhibited conversion efficiency values as high as 5% or more, particularly when compounds CA3 to CA6, CB2 to CB6, CC3 to CC6, CD3 to CD6, F1, F2, G1, M2 to M4, N1 to N4, O1, P1, Q1, R1 to R4, S1, S2, T2, T3, U1 to U3, V1, Z2 to Z4, ⁇ 2 to ⁇ 4, ⁇ 2 to ⁇ 4, ⁇ 2 and ⁇ 3 were used as the dye, as shown in Tables 1-3 to 1-5. Even when ones having other structure than the structures described above were used as the dye, the conversion efficiency was at a practically usable level of equal to or more than 2% and less than 5%.
  • Comparative Example of Sample No. 92 had a conversion efficiency of equal to or more than 0.5% and less than 2%, and was unsatisfactory to be used in electrochemical cells.
  • An ITO film was produced on a glass substrate, and an FTO film was laminated thereon. Thus, a transparent conductive film was produced. Thereafter, an oxide semiconductor porous film was formed on the transparent conductive film, and thus a transparent electrode plate was obtained.
  • This transparent electrode plate was used, and the dye of the second embodiment of the present invention described above was used, to produce a photoelectrochemical cell. The conversion efficiencies of the photoelectrochemical cells were measured. The measurement is performed as described in the following steps (1) to (5).
  • the surface of a heat resistant glass plate having a thickness of 2 mm was subjected to chemical cleaning and was dried. Subsequently, this glass plate was placed in a reactor and was heated with a heater. When the heating temperature of the heater reached 450° C., the raw material compound solution for ITO film obtained in the step (1) was sprayed over the glass plate for 25 minutes through a nozzle having an aperture diameter of 0.3 mm at a pressure of 0.06 MPa with a distance to the glass plate of 400 mm.
  • a transparent electrode plate having only an ITO film having a thickness of 530 nm formed on a heat resistant glass plate having a thickness of 2 mm, and a transparent electrode plate having only an FTO film having a thickness of 180 nm formed in the same manner were respectively produced.
  • photoelectrochemical cells having a structure such as shown in FIG. 2 of Japanese Patent No. 4260494 were produced using the three kinds of transparent electrode plates.
  • the formation of an oxide semiconductor porous film 15 was carried out by dispersing titanium oxide fine particles having an average particle size of about 230 nm in acetonitrile to prepare a paste, applying this paste on a transparent electrode 11 by a bar coating method to a thickness of 15 ⁇ m, drying the paste, and then calcining the paste at 450° C. for one hour.
  • the dyes indicated in Table 2 were loaded in this oxide semiconductor porous film 15.
  • the conditions for immersion in a dye solution were the same as those used in Example 1-1.
  • a conductive substrate produced by laminating an ITO film and an FTO film on a glass plate was used for the counter electrode 16, and an electrolytic liquid formed from a non-aqueous solution of iodine/iodide was used in the electrolyte layer 17.
  • the plane dimension of the photoelectrochemical cell was 25 mm ⁇ 25 mm
  • a collector electrode was disposed on the FTO film, and thus a photoelectrochemical cell was produced. The conversion efficiency was evaluated.
  • the dye of the first embodiment of the present invention prepared as described above was used as the dye.
  • the evaluation was performed using two kinds of photoelectrochemical cells of a test cell (i) and a test cell (iv), as follows.
  • the surface of a heat resistant glass plate having a size of 100 mm ⁇ 100 mm ⁇ 2 mm was subjected to chemical cleaning and was dried. Subsequently, this glass plate was placed in a reactor and was heated with a heater. Subsequently, the raw material compound solution for FTO film (fluorine-doped tin oxide) used in Example 2-1 was sprayed on the glass plate for 25 minutes through a nozzle having an aperture diameter of 0.3 mm at a pressure of 0.06 MPa, with a distance to the glass plate of 400 mm, and thus an FTO film-attached glass plate was prepared. Grooves having a depth of 5 ⁇ m were formed on that surface in the form of a lattice circuit pattern by an etching method.
  • FTO film fluorine-doped tin oxide
  • a pattern was formed by photolithography, and then etching was performed using hydrofluoric acid.
  • a metal conductive layer (seed layer) was formed thereon by a sputtering method for the purpose of enabling plating formation, and a metal wiring layer 3 was further formed thereon by additive plating.
  • the metal wiring layer 3 was formed in a convex lens shape to a height of 3 ⁇ m from the surface of the transparent substrate 2.
  • the circuit width was set to 60 ⁇ m.
  • An FTO film was formed over the metal wiring layer 3 by a SPD method to a thickness of 400 nm as a shielding layer 5, and the final assembly was used as an electrode substrate (i).
  • the cross-sectional shape of the electrode substrate (i) was as shown in FIG. 2 of JP-A-2004-146425.
  • a dispersion liquid of titanium oxide having an average particle size of 25 nm was applied and dried on the electrode substrate (i), and the electrode substrate was heated and sintered at 450° C. for one hour.
  • This electrode substrate was immersed in each of the ethanol solutions of the dyes indicated in Table 3 to adsorb the dye.
  • the conditions for immersion were the same as those used in Example 1.
  • the electrode substrate and a platinum sputtered FTO substrate were arranged to face each other, with a thermoplastic polyolefin resin sheet having a thickness of 50 ⁇ m interposed therebetween, and the resin sheet portion was melted by heating to fix the two electrode substrates.
  • a methoxyacetonitrile solution containing an iodide salt at 0.5 M and iodine at 0.05 M as main components was injected through an injection port for electrolytic liquid, which had been kept open in advance on the platinum sputtered electrode side, and the methoxyacetonitrile solution was filled in between the electrodes. Furthermore, the peripheral areas and the electrolytic liquid injection port were fully sealed using an epoxy-based sealing resin, and a silver paste was applied on the collecting terminal portions. Thus, a test cell (i) was prepared. The photoelectric conversion characteristics of the test cell (i) were evaluated by using pseudo-sunlight of AM1.5. The results are presented in Table 3-1.
  • An FTO film-attached glass substrate having a size of 100 ⁇ 100 mm was produced in the same manner as in the case of the test cell (i).
  • a metal wiring layer 3 (gold circuit) was formed on that FTO glass substrate by an additive plating method.
  • the metal wiring layer 3 (gold circuit) was formed in a lattice form on the substrate surface, and the metal wiring layer had a circuit width of 50 ⁇ m and a circuit thickness of 5 ⁇ m.
  • An FTO film having a thickness of 300 nm was formed on this surface by an SPD method as a shielding layer 5 , and thus the final assembly was used as a test cell (iv).
  • the cross-section of the electrode substrate (iv) was examined using SEM-EDX, and there was slippage which was thought to be attributable to the footing of the plating resist at the wiring bottom, while FTO coating was not provided on shaded areas.
  • a test cell (iv) was produced in the same manner as in the case of the test cell (i), using the electrode substrate (iv).
  • the photoelectric conversion characteristics of the test cell (iv) were evaluated by using pseudo-sunlight of AM 1.5.
  • the results are presented in Table 3. The results are represented such that one having a conversion efficiency of 5% or more is indicated with “ ⁇ circle around (•) ⁇ ”; one having a conversion efficiency of equal to or more than 2% and less than 5% is indicated with “ ⁇ ”; one having a conversion efficiency of equal to or more than 0.5% and less than 2% is indicated with “ ⁇ ”; and one having a conversion efficiency of less than 0.5% is indicated with “x”.
  • Example 3-1 An evaluation was performed in the same manner as in Example 3-1, using the dye of the second embodiment of the present invention prepared as described above. The results are presented in Table 3-2.
  • titania colloidal particles (A) were prepared.
  • the titania colloidal particles thus obtained were composed of anatase type titanium oxide having high crystallinity as determined by X-ray diffraction.
  • the titania colloidal particles (A) obtained as described above were concentrated to 10% by mass, and were mixed with the peroxotitanic acid solution.
  • the amount of titanium in the mixed liquid was calculated in terms of TiO 2
  • hydroxypropyl cellulose was added to the mixture as a film forming aid, such that the amount of hydroxypropyl cellulose reached 30% by mass relative to the mass of TiO 2 .
  • a coating liquid for semiconductor film formation was prepared.
  • the coating liquid was applied on a transparent glass substrate on which fluorine-doped tin oxide was formed as an electrode layer, and was naturally dried.
  • the coating liquid was then irradiated with ultraviolet radiation in an amount of 6000 mJ/cm 2 using a low pressure mercury lamp to decompose peroxo acid, and thereby the coating film was cured.
  • the coating film was heated at 300° C. for 30 minutes, and thereby decomposition of hydroxypropyl cellulose and annealing were carried out.
  • an oxide semiconductor film (A) was formed on the glass substrate.
  • an ethanol solution of a dye of the present invention at a concentration of 3 ⁇ 10 ⁇ 4 mol/Liter was prepared as a spectral sensitizing dye.
  • This dye solution was applied on the metal oxide semiconductor film (A) with a 100-rpm spinner, and was dried. This application and drying processes were repeated five times.
  • the lateral sides were sealed with a resin, and the electrolyte solution of step (4) was included between the electrodes. Furthermore, lead wires were connected between the electrodes, and thus a photoelectric cell (A) was produced.
  • the photoelectric cell (A) was irradiated with light with an intensity of 100 W/m 2 using a solar simulator, and ⁇ (conversion efficiency) was measured.
  • the results are presented in Table 4-1.
  • An oxide semiconductor film (B) was formed in the same manner as in the case of the oxide semiconductor film (A), except that the film was cured by irradiating with ultraviolet radiation to decompose peroxo acid, and then the film was irradiated with ions of Ar gas (manufactured by Nissin Electric Co., Ltd.: ion injection device, irradiated at 200 eV for 10 hours).
  • Adsorption of a dye on the oxide semiconductor film (B) was carried out in the same manner as in the case of the oxide semiconductor film (A).
  • titania colloidal particles (C) were prepared.
  • an oxide semiconductor film (C) was formed in the same manner as in the case of the oxide semiconductor film (A), using the peroxotitanic acid solution and the titania colloidal particles (C) obtained as described above.
  • Adsorption of a dye of the present invention as a spectral sensitizing dye was carried out in the same manner as in the case of the metal oxide semiconductor film (A).
  • the titania colloidal particles (D) were concentrated to 10% by mass, and hydroxypropyl cellulose was added to the particles as a film forming aid such that the amount of hydroxypropyl cellulose reached 30% by mass in terms of TiO 2 .
  • a coating liquid for semiconductor film formation was prepared.
  • the coating liquid was applied on a transparent glass substrate on which fluorine-doped tin oxide was formed as an electrode layer, and was naturally dried.
  • the coating liquid was irradiated with ultraviolet radiation in an amount of 6000 mJ/cm 2 using a low pressure mercury lamp, and thereby the film was cured.
  • the film was further heated at 300° C. for 30 minutes to perform decomposition of hydroxypropyl cellulose and annealing.
  • an oxide semiconductor film (D) was formed.
  • a photoelectric cell (D) was produced by the same method as that used for the photoelectric cell (A), and ⁇ was measured.
  • the results are presented in Table 4-1. The results are represented such that one having a conversion efficiency of 5% or more is indicated with “ ⁇ circle around (•) ⁇ ”; one having a conversion efficiency of equal to or more than 2% and less than 5% is indicated with “ ⁇ ”; one having a conversion efficiency of equal to or more than 0.5% and less than 2% is indicated with “ ⁇ ”; and one having a conversion efficiency of less than 0.5% is indicated with “x”.
  • the preparation or synthesis of titanium oxide was carried out by varying the method, and an oxide semiconductor film was produced from the titanium oxide thus obtained.
  • a photoelectrochemical cell was produced using the oxide semiconductor film, and an evaluation of the cell was performed.
  • the dye of the first embodiment of the present invention prepared as described above, was used as the dye.
  • anatase type titanium oxide manufactured by Ishihara Sangyo Kaisha, Ltd., trade name: ST-01
  • this product was heated to about 900° C. to convert it to brookite type titanium oxide, and was further heated to about 1,200° C. to convert it to rutile type titanium oxide.
  • comparative titanium oxide 1 anatase type
  • titanium oxide 1 brookite type
  • comparative titanium oxide 2 rutile type
  • a reaction tank equipped with a reflux condenser was charged with 954 ml of distilled water, and the distilled water was heated to 95° C. While the stirring speed was maintained at about 200 rpm, 46 ml of an aqueous solution of titanium tetrachloride (Ti content: 16.3% by mass, specific gravity 1.59, purity 99.9%) was added dropwise to this distilled water in the reaction tank at a rate of about 5.0 ml/min. At this time, caution was taken to prevent the temperature of the reaction liquid from falling. As a result, the concentration of titanium tetrachloride was 0.25 mol/liter (2% by mass in terms of titanium oxide).
  • reaction liquid began to turn cloudy immediately after the dropwise addition, but the reaction liquid was maintained at that temperature. After completion of the dropwise addition, the temperature was further increased to heat the reaction liquid close to the boiling point (104° C.), and the reaction liquid was maintained in this state for 60 minutes to completely terminate the reaction.
  • a sol obtained by the reaction was filtered, and then the sol was made into a powder using a vacuum dryer at 60° C.
  • This powder was quantitatively analyzed by an X-ray diffraction method.
  • the ratio of (peak intensity of the brookite type 121 plane)/(peak intensity at the position where the three types overlap) was 0.38
  • the ratio of (main peak intensity of the rutile type)/(peak intensity at the position where the three types overlap) was 0.05.
  • the titanium oxide was crystalline, composed of about 70.0% by mass of the brookite type, about 1.2% by mass of the rutile type, and about 28.8% by mass of the anatase type.
  • the fine particles were observed with a transmission electron microscope, and the average particle size of the primary particles was 0.015 ⁇ m.
  • aqueous solution of titanium trichloride (Ti content: 28% by mass, specific gravity 1.5, purity 99.9%) was diluted with distilled water, and a solution at a concentration of 0.25 mol/L in terms of titanium was obtained. At this time, the solution was ice-cooled to prevent the temperature of the liquid from rising, and thus the solution was maintained at 50° C. or below. Subsequently, 500 ml of this solution was introduced into a reaction tank equipped with a reflux condenser, and while this solution was heated to 85° C., ozone gas with a purity of 80% generated from a ozone gas generating apparatus was bubbled into the solution at a rate of 1 L/min to induce an oxidation reaction.
  • the system was maintained in this state for 2 hours, and thus the reaction was completely terminated.
  • a sol thus obtained was filtered and dried in a vacuum to obtain a powder.
  • This powder was quantitatively analyzed by an X-ray diffraction method.
  • the ratio of (peak intensity of the brookite type 121 plane)/(peak intensity at the position where the three types overlapped) was 0.85
  • the ratio of (main peak intensity of the rutile type)/(peak intensity at the position where the three types overlapped) was 0.
  • the titanium dioxide was composed of about 98% by mass of the brookite type, 0% by mass of the rutile type, 0% by mass of the anatase type, and about 2% of amorphous titanium dioxide.
  • the fine particles were observed with a transmission electron microscope, and the average particle size of the primary particles was 0.05 ⁇ m.
  • titanium oxides prepared in the above-described sections “Titanium oxide 1” to “Titanium oxide 3” were used as semiconductor, and photoelectric conversion elements having a configuration as shown in FIG. 1 of JP-A-2000-340269 were produced as follows.
  • Fluorine-doped tin oxide was coated on a glass substrate, and this was used as a conductive transparent electrode.
  • a paste containing each type of the titanium oxide particles as a raw material was prepared, and the paste was applied on the electrode surface by a bar coating method to a thickness of 50 ⁇ m. Subsequently, the paste was calcined at 500° C., and thus a thin layer having a thickness of about 20 ⁇ m was formed.
  • An ethanol solution of the dye at a molar concentration of 3 ⁇ 10 4 M was prepared, and the glass substrate on which a thin layer of titanium oxide was formed was immersed in this ethanol solution and was maintained therein for 12 hours at room temperature. As a result, the dye was adsorbed on the thin layer of titanium oxide.
  • results are represented such that one having a conversion efficiency of 5% or more is indicated with “ ⁇ circle around (•) ⁇ ”; one having a conversion efficiency of equal to or more than 2% and less than 5% is indicated with “ ⁇ ”; one having a conversion efficiency of equal to or more than 0.5% and less than 2% is indicated with “ ⁇ ”; and one having a conversion efficiency of less than 0.5% is indicated with “x”.
  • Example 5-1 An evaluation was performed in the same manner as in Example 5-1, using the dye of the second embodiment of the present invention prepared as described above. The results are presented in Table 5-2.
  • Photoelectrochemical cells were produced by using titanium oxide particles having different particle sizes for the semiconductor electrodes, and their characteristics were evaluated.
  • the dye of the first embodiment of the present invention prepared as described above was used as the dye.
  • a paste for forming a semiconductor layer or a light scattering layer for a semiconductor electrode that constitutes a photoelectrode was prepared by the following procedure.
  • Spherical-shaped TiO 2 particles (anatase type, average particle size: 25 nm; hereinafter, referred to as spherical TiO 2 particles 1) were introduced into a nitric acid solution and stirred. Thus, a titania slurry was prepared. Subsequently, a cellulose-based binder was added to the titania slurry as a thickening agent, and the mixture was kneaded. Thus, a paste was prepared.
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 100 nm, aspect ratio: 5; hereinafter, referred to as rod-shaped TiO 2 particles 1), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 1 to the mass of the paste 1 of 10:90 was prepared.
  • rod-shaped TiO 2 particles anatase type, diameter: 100 nm, aspect ratio: 5; hereinafter, referred to as rod-shaped TiO 2 particles 1
  • a paste having a ratio of the mass of the rod-shaped TiO 2 particles 1 to the mass of the paste 1 of 10:90 was prepared.
  • the paste 1 was mixed with the rod-shaped TiO 2 particles 1, and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 1 to the mass of the paste 1 of 30:70 was prepared.
  • the paste 1 was mixed with the rod-shaped TiO 2 particles 1, and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 1 to the mass of the paste 1 of 50:50 was prepared.
  • the paste 1 was mixed with plate-shaped mica particles (diameter: 100 nm, aspect ratio: 6; hereinafter, referred to as plate-shaped mica particles 1), and thus a paste having a ratio of the mass of the plate-shaped mica particles 1 to the mass of the paste 1 of 20:80 was prepared.
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 30 nm, aspect ratio: 6.3; hereinafter, referred to as rod-shaped TiO 2 particles 2), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 2 to the mass of the paste 1 of 30:70 was prepared.
  • rod-shaped TiO 2 particles anatase type, diameter: 30 nm, aspect ratio: 6.3; hereinafter, referred to as rod-shaped TiO 2 particles 2
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 50 nm, aspect ratio: 6.1; hereinafter, referred to as rod-shaped TiO 2 particles 3), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 3 to the mass of the paste 1 of 30:70 was prepared.
  • rod-shaped TiO 2 particles anatase type, diameter: 50 nm, aspect ratio: 6.1; hereinafter, referred to as rod-shaped TiO 2 particles 3
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 75 nm, aspect ratio: 5.8; hereinafter, referred to as rod-shaped TiO 2 particles 4), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 4 to the mass of the paste 1 of 30:70 was prepared.
  • rod-shaped TiO 2 particles anatase type, diameter: 75 nm, aspect ratio: 5.8; hereinafter, referred to as rod-shaped TiO 2 particles 4
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 130 nm, aspect ratio: 5.2; hereinafter, referred to as rod-shaped TiO 2 particles 5), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 5 to the mass of the paste 1 of 30:70 was prepared.
  • rod-shaped TiO 2 particles anatase type, diameter: 130 nm, aspect ratio: 5.2; hereinafter, referred to as rod-shaped TiO 2 particles 5
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 180 nm, aspect ratio: 5; hereinafter, referred to as rod-shaped TiO 2 particles 6), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 6 to the mass of the paste 1 of 30:70 was prepared.
  • rod-shaped TiO 2 particles anatase type, diameter: 180 nm, aspect ratio: 5; hereinafter, referred to as rod-shaped TiO 2 particles 6
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 240 nm, aspect ratio: 5; hereinafter, referred to as rod-shaped TiO 2 particles 7), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 7 to the mass of the paste 1 of 30:70 was prepared.
  • rod-shaped TiO 2 particles 7 anatase type, diameter: 240 nm, aspect ratio: 5; hereinafter, referred to as rod-shaped TiO 2 particles 7
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 110 nm, aspect ratio: 4.1; hereinafter, referred to as rod-shaped TiO 2 particles 8), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 8 to the mass of the paste 1 of 30:70 was prepared.
  • rod-shaped TiO 2 particles anatase type, diameter: 110 nm, aspect ratio: 4.1; hereinafter, referred to as rod-shaped TiO 2 particles 8
  • the paste 1 was mixed with rod-shaped TiO 2 particles (anatase type, diameter: 105 nm, aspect ratio: 3.4; hereinafter, referred to as rod-shaped TiO 2 particles 9), and thus a paste having a ratio of the mass of the rod-shaped TiO 2 particles 9 to the mass of the paste 1 of 30:70 was prepared.
  • rod-shaped TiO 2 particles anatase type, diameter: 105 nm, aspect ratio: 3.4; hereinafter, referred to as rod-shaped TiO 2 particles 9
  • a photoelectrode having the same configuration as that of the photoelectrode 12 shown in FIG. 5 of JP-A-2002-289274 was produced by the procedure described below, and using this photoelectrode, a photoelectrochemical cell 1 which has a dimension of 10 ⁇ 10 mm and has the same configuration as that of the dye-sensitized solar cell 20 except for the photoelectrode, was produced.
  • a dye was adsorbed on the semiconductor electrode as follows. First, anhydrous ethanol which had been dehydrated with magnesium ethoxide was used as a solvent, and the dye of the present invention was dissolved in this anhydrous ethanol to a concentration of 3 ⁇ 10 ⁇ 4 mol/L. Thus, a dye solution was prepared. Subsequently, the semiconductor electrode was immersed in this solution, and thereby, the dye was adsorbed on the semiconductor electrode in an amount of about 1.5 mmol/m 2 . Thus, a photoelectrode 10 was completed.
  • a platinum electrode (thickness of Pt thin film: 100 nm) having the same shape and size as those of the photoelectrode described above was produced as a counter electrode, and an iodine-based redox solution containing iodine and lithium iodide was prepared as an electrolyte E.
  • a spacer-S (trade name: “Surlyn”) manufactured by DuPont Company, which had a shape matching the size of the semiconductor electrode, was prepared.
  • the photoelectrode 10 and the counter electrode CE were arranged to face each other, with the spacer-S interposed therebetween, and the electrolyte described above was filled in the inside.
  • a photoelectrochemical cell 1 was completed.
  • a photoelectrode having the same configuration as that of the photoelectrode 10 shown in FIG. 1 of JP-A-2002-289274, and a photoelectrochemical cell 2 having the same configuration as that of the dye-sensitized solar cell 20 shown in FIG. 3 of JP-A-2002-289274 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the production of the semiconductor electrode was carried out in the manner described below.
  • the paste 2 was used as a paste for semiconductor layer formation.
  • the paste 2 was applied on the SnO 2 conductive film by screen printing, and then was dried.
  • the paste was calcined under the conditions of 450° C. in air, and thus a semiconductor layer was formed.
  • the paste 3 was used as a paste for the innermost layer formation of the light scattering layer. Also, the paste 5 was used as a paste for the outermost layer formation of the light scattering layer. Then, a light scattering layer was formed on the semiconductor layer in the same manner as in the case of the dye-sensitized solar cell 1.
  • a semiconductor electrode (area of light-receiving surface: 10 mm ⁇ 10 mm, layer thickness: 10 ⁇ m, thickness of semiconductor layer: 3 ⁇ m, thickness of the innermost layer: 4 ⁇ m, content ratio of the rod-shaped TiO 2 particles 1 contained in the innermost layer: 10% by mass, thickness of the outermost layer: 3 ⁇ m, and content ratio of the rod-shaped TiO 2 particles 1 contained in the innermost layer: 50% by mass) having the same configuration as that of the semiconductor electrode 2 shown in FIG. 1 of JP-A-2002-289274 was formed on the SnO 2 conductive film. Thus, a photoelectrode that did not contain a sensitizing dye was produced.
  • a photoelectrode having the same configuration as that of the photoelectrode 10 shown in FIG. 5, and a photoelectrochemical cell 3 having the same configuration as that of the photoelectrochemical cell 20 shown in FIG. 3 described in JP-A-2002-289274 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 1 was used as the paste for semiconductor layer formation, and the paste 4 was used as the paste for light scattering layer formation.
  • the semiconductor electrode had a configuration as follows: area of the light receiving surface: 10 mm ⁇ 10 mm, layer thickness: 10 ⁇ m, thickness of the semiconductor layer: 5 ⁇ m, thickness of light scattering layer: 5 ⁇ m, and content ratio of the rod-shaped TiO 2 particles 1 contained in the light scattering layer: 30% by mass.
  • a photoelectrode having the same configuration as that of the photoelectrode 10 shown in FIG. 5, and a photoelectrochemical cell 4 having the same configuration as that of the photoelectrochemical cell 20 shown in FIG. 3 described in JP-A-2002-289274 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 2 was used as the paste for semiconductor layer formation, and the paste 6 was used as the paste for light scattering layer formation.
  • the semiconductor electrode had a configuration as follows: area of the light receiving surface: 10 mm ⁇ 10 mm, layer thickness: 10 ⁇ m, thickness of the semiconductor layer: 6.5 ⁇ m, thickness of light scattering layer: 3.5 ⁇ m, and content ratio of the plate-shaped mica particles 1 contained in the light scattering layer: 20% by mass.
  • a photoelectrode and a photoelectrochemical cell 5 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 2 was used as the paste for semiconductor layer formation, and the paste 8 was used as the paste for light scattering layer formation.
  • the content ratio of the rod-shaped TiO 2 particles 3 contained in the light scattering layer of the semiconductor electrode 30% by mass.
  • a photoelectrode and a photoelectrochemical cell 6 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 2 was used as the paste for semiconductor layer formation, and the paste 9 was used as the paste for light scattering layer formation.
  • the content ratio of the rod-shaped TiO 2 particles 4 contained in the light scattering layer of the semiconductor electrode 30% by mass.
  • a photoelectrode and a photoelectrochemical cell 7 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 2 was used as the paste for semiconductor layer formation, and the paste 10 was used as the paste for light scattering layer formation.
  • the content ratio of the rod-shaped TiO 2 particles 5 contained in the light scattering layer of the semiconductor electrode 30% by mass.
  • a photoelectrode and a photoelectrochemical cell 8 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 2 was used as the paste for semiconductor layer formation, and the paste 11 was used as the paste for light scattering layer formation.
  • the content ratio of the rod-shaped TiO 2 particles 6 contained in the light scattering layer of the semiconductor electrode 30% by mass.
  • a photoelectrode and a photoelectrochemical cell 9 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 2 was used as the paste for semiconductor layer formation, and the paste 13 was used as the paste for light scattering layer formation.
  • the content ratio of the rod-shaped TiO 2 particles 8 contained in the light scattering layer of the semiconductor electrode 30% by mass.
  • a photoelectrode and a photoelectrochemical cell 10 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 2 was used as the paste for semiconductor layer formation, and the paste 14 was used as the paste for light scattering layer formation.
  • the content ratio of the rod-shaped TiO 2 particles 9 contained in the light scattering layer of the semiconductor electrode 30% by mass.
  • a photoelectrode and a comparative photoelectrochemical cell 1 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that a semiconductor electrode (area of light-receiving surface: 10 mm ⁇ 10 mm, and layer thickness: 10 ⁇ m) having only a semiconductor layer was produced using only the paste 2.
  • a photoelectrode and a comparative photoelectrochemical cell 2 were produced by the same procedure as that used for the photoelectrochemical cell 1, except that the paste 2 was used as the paste for semiconductor layer formation, and the paste 7 was used as the paste for light scattering layer formation.
  • the content ratio of the rod-shaped TiO 2 particles 2 contained in the light scattering layer of the semiconductor electrode 30% by mass.
  • a cell characterization test was carried out, and the conversion efficiencies 11 of the photoelectrochemical cells 1 to 10, and comparative photoelectrochemical cells 1 and 2 were measured.
  • the cell characteristics evaluation test was carried out using a solar simulator (manufactured by Wacom Electric Co., Ltd., WXS-85-H type), under the measurement conditions in which the condition for irradiation with pseudo-sunlight from a xenon lamp through an AM1.5 filter was set at 100 mW/cm 2 .
  • the current-voltage characteristics were measured using an I-V tester, and the energy conversion efficiency ⁇ [%] was determined. The results are shown in Table 6-1.
  • results are represented such that one having a conversion efficiency of 5% or more is indicated with “ ⁇ circle around (•) ⁇ ”; one having a conversion efficiency of equal to or more than 2% and less than 5% is indicated with “ ⁇ ”; one having a conversion efficiency of equal to or more than 0.5% and less than 2% is indicated with “ ⁇ ”; and one having a conversion efficiency of less than 0.5% is indicated with “x”.
  • a metal alkoxide was added to the metal oxide fine particles, and the mixture was made into a slurry.
  • the slurry was applied on a conductive substrate, and then the slurry was subjected to irradiation with UV ozone, irradiation with UV and/or drying, and thus electrodes were produced. Thereafter, photoelectrochemical cells were produced, and the conversion efficiencies were measured.
  • the dye of the first embodiment of the present invention prepared as described above was used as the dye.
  • Titanium oxide was used for the metal oxide fine particles.
  • P25 powder manufactured by Degussa GmbH, trade name which is composed of 30% of the rutile type and 70% of the anatase type on a mass basis, and has an average particle size of 25 nm, was used.
  • the metal oxide fine particles were heat-treated in advance, and thereby organic materials and moisture on the surface were eliminated.
  • the particles were heated for 30 minutes in an oven at 450° C. in open air.
  • the amounts of moisture contained in the titanium oxide and the P25 powder (manufactured by Degussa GmbH, trade name), which had been stored in an environment at a temperature of 26° C. and a humidity of 72%, were quantitatively measured by weight reduction during thermal weight measurement and by Karl Fischer titration of the amount of moisture desorbed when heated to 300° C.
  • niobium (V) pentaethoxide as a niobium raw material all manufactured by Sigma-Aldrich Company
  • the molar concentration ratio of the metal oxide fine particles and the metal alkoxide was appropriately adjusted in accordance with the metal oxide fine particle diameter, so that the amorphous layer produced as a result of hydrolysis of the metal alkoxide would not become excessively thick, and binding between the particles could be sufficiently achieved.
  • the metal alkoxides were all used in the form of a 0.1 M ethanol solution.
  • TTIP titanium (IV) tetraisopropoxide
  • 3.55 g of a 0.1 M TTIP solution was mixed with 1 g of the titanium oxide fine particles.
  • the concentration of titanium oxide in the paste thus obtained was about 22% by mass, and the paste had a viscosity appropriate for application.
  • the ratio of titanium oxide, TTIP and ethanol was 1:0.127:3.42 on a mass basis, and 1:0.036:5.92 on a molar basis.
  • mixed pastes of titanium oxide fine particles and alkoxides other than TTIP were also prepared such that the concentration of the fine particles was 22% by mass.
  • the concentration of the fine particles was set to 16% by mass.
  • the metal alkoxide solution was mixed at a ratio of 5.25 g to 1 g of the metal oxide fine particles.
  • the metal oxide fine particles and the metal alkoxide solution were stirred with a magnetic stirrer for 2 hours in a sealed container, and thus a uniform paste was obtained.
  • a doctor blade method a screen printing method, a spray coating method or the like can be used, and an appropriate paste viscosity was appropriately selected according to the application method.
  • a method of applying the paste with a glass rod (similar to the doctor blade method) was conveniently used.
  • the concentration of the metal oxide fine particles that resulted in an appropriate paste viscosity was approximately in the range of 5% to 30% by mass.
  • the thickness of the layer of amorphous metal oxide that was produced as a result of decomposition of the metal alkoxide was in the range of about 0.1 to 0.6 nm in the present Example. Generally, the range of about 0.05 to 1.3 nm was appropriate for the film formation at room temperature according to the present technique.
  • a porous film was produced, prior to dye adsorption, by changing the conditions on the presence or absence of a UV ozone treatment, a UV irradiation treatment and/or a drying treatment.
  • the film obtained after the application on the conductive substrate was air dried in open air at room temperature for about 2 minutes.
  • the metal alkoxides in the pastes were hydrolyzed due to the moisture in air, and titanium oxide, zirconium oxide, and niobium oxide, all being amorphous, were formed respectively from Ti alkoxide, Zr alkoxide, and Nb alkoxide.
  • a UV ozone cleaner, NL-UV253, manufactured by Nippon Laser Electronics Lab Co., Ltd. was used for the UV ozone treatment.
  • the UV light source included three 4.5-W mercury lamps each having emission lines at 185 nm and 254 nm, and the sample was disposed horizontally at a distance of about 6.5 cm from the light source.
  • an oxygen gas stream is introduced into the chamber, ozone is generated.
  • this UV ozone treatment was carried out for 2 hours. No decrease was observed in the conductivity of the ITO film and the FTO film due to this UV ozone treatment.
  • the UV treatment was carried out for 2 hours in the same manner as in the UV ozone treatment, except that the treatment was performed by purging the chamber with nitrogen. No decrease was observed in the conductivity of the ITO film and the FTO film due to this UV treatment.
  • a 0.5 mM ethanol solution was prepared using a dye of the present invention.
  • a porous film produced by the process described above was dried for one hour in an oven at 100° C., and then was immersed in a solution of the sensitizing dye. The porous film was left immersed at room temperature for 50 minutes, so that the sensitizing dye was adsorbed on the surface of titanium oxide.
  • the sample after the adsorption of the sensitizing dye was washed with ethanol and was air dried.
  • the conductive substrate in which a porous film was formed after dye adsorption was used as a photoelectrode, and this photoelectrode and an ITO/PET film or FTO/glass counter electrode which had been modified with platinum fine particles by sputtering, were arranged to face each other.
  • a photoelectrochemical cell was produced.
  • the effective area of the photoelectrode was adjusted to about 0.2 cm 2 .
  • a 3-methoxypropionitrile solution containing 0.5M LiI, 0.05M I 2 , and 0.5M t-butylpyridine was used as an electrolyte solution, and this solution was introduced into the gap between the two electrodes by means of the capillary phenomenon.
  • the evaluation of the cell performance was carried out by the measurement of a photocurrent action spectrum under irradiation with a definite number of photons (1016 cm ⁇ 2 ), and by I-V measurement under irradiation with AM1.5 pseudo-sunlight (100 mW/cm 2 ). These measurements were carried out using a CEP-2000 type spectral response measurement apparatus manufactured by Bunkoukeiki Co., Ltd.
  • the column for the item “Pre-treatment of TiO 2 ” in Table 7-1 represents the presence or absence of a pretreatment (heat treatment for 30 minutes in an oven at 450° C.) of the titanium oxide fine particles.
  • Samples 6, 14 and 22 represent samples obtained by using a paste with a high TTIP concentration (the molar ratio of titanium oxide:TTIP was 1:0.356).
  • the other samples (samples 1 to 5, 7 to 13, 23 and 24) were all obtained by using a paste having a molar ratio of titanium oxide:TTIP of 1:0.0356.
  • the column for the item “Pre-treatment of TiO 2 ” in Table 7-2 represents the presence or absence of a pretreatment (heat treatment for 30 minutes in an oven at 450° C.) of the titanium oxide fine particles.
  • Samples 6, 14 and 22 represent samples obtained by using a paste with a high TTIP concentration (the molar ratio of titanium oxide:TTIP was 1:0.356).
  • the other samples (samples 1 to 5, 7 to 13, 23 and 24) were all obtained by using a paste having a molar ratio of titanium oxide:TTIP of 1:0.0356.
  • the column for the item “Pre-treatment of TiO 2 ” in Table 7-3 represents the presence or absence of a pretreatment (heat treatment for 30 minutes in an oven at 450° C.) of the titanium oxide fine particles.
  • Samples 6, 14 and 22 represent samples obtained by using a paste with a high TTIP concentration (the molar ratio of titanium oxide:TTIP was 1:0.356).
  • the other samples (samples 1 to 5, 7 to 13, 23 and 24) were all obtained by using a paste having a molar ratio of titanium oxide:TTIP of 1:0.0356.
  • An electrolyte solution in which 0.1 mol/L of lithium iodide, 0.05 mol/L of iodine, and 0.62 mol/L of dimethylpropylimidazolium iodide were dissolved was prepared using acetonitrile as a solvent.
  • the benzimidazole-based compounds of No. 1 to No. 8 shown below were separately added so as to be a concentration of 0.5 mol/L each, and the compounds were dissolved therein.
  • a conductive film was formed on a glass substrate by sputtering fluorine-doped tin oxide as a transparent conductive film.
  • a dispersion liquid containing anatase type titanium oxide particles (a dispersion liquid of semiconductor fine particles obtained by incorporating 32 g of anatase type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) into 100 mL of a mixed solvent composed of water and acetonitrile at a volume ratio of 4:1, and uniformly dispersing and mixing the mixture using a rotation/revolution combination type mixing conditioner) was applied, and was sintered.
  • the dye of the first embodiment of the present invention was adsorbed thereon, and thus a photosensitive layer having a thickness of 15 ⁇ m was formed.
  • the electrolytic liquid of the benzimidazole-based compounds of No. 1 to No. 8 was added dropwise to the photosensitive layer.
  • a frame type spacer (thickness 25 ⁇ m) made of a polyethylene film was mounted thereon, and this spacer was covered with a platinum counter electrode. Thus, a photoelectric conversion element was produced.
  • Photoelectric conversion elements thus obtained were irradiated with light at an intensity of 100 mW/cm 2 using a Xe lamp as a light source.
  • the open circuit voltages and photoelectric conversion efficiencies thus obtained are shown in Table 8-1.
  • the results are presented such that one having an open circuit voltage of 7.0 V or more is indicated with “ ⁇ circle around (•) ⁇ ”; one having an open circuit voltage of equal to or more than 6.5 V and less than 7.0 is indicated with “ ⁇ ”; one having an open circuit voltage of equal to or more than 6.0 V and less than 6.5 V is indicated with “ ⁇ ”; and one having an open circuit voltage of less than 6.0 V is indicated with “x”.
  • Table 8-1 also shows the results obtained with a photoelectric conversion element which used an electrolytic liquid without any added benzimidazole-based compound.
  • Example 8-1 An evaluation was performed in the same manner as in Example 8-1, using the dye of the third embodiment of the present invention that was prepared as described above. The results are presented in Table 8-3. It was understood from Table 8-3 that the dyes of the present invention provide high conversion efficiencies.
  • a photoelectrode having the same configuration as that of the photoelectrode 10 shown in FIG. 1 described in JP-A-2004-152613 was produced by the procedure shown below. Further, a photoelectrochemical cell (area of the light-receiving surface F2 of the semiconductor electrode 2: 1 cm 2 ) having the same configuration as that of the dye-sensitized solar cell 20 shown in FIG. 1 described in JP-A-2004-152613, except for the use of the above-described photoelectrode, was produced.
  • the layer disposed closer to the transparent electrode 1 is referred to as a “first layer”
  • the layer disposed closer to the porous substance layer PS is referred to as a “second layer”.
  • slurry 1 a slurry for second layer formation
  • slurry 2 a slurry for first layer formation (content of P1: 15% by mass; hereinafter, referred to as “slurry 2”) was prepared by the same production procedure as that used for the slurry 1, except that only P25 was used, without using P200.
  • a transparent electrode in which a fluorine-doped SnO 2 conductive film (thickness: 700 nm) was formed on a glass substrate (transparent conductive glass), was prepared.
  • the slurry 2 described above was applied on this SnO 2 conductive film with a bar coater, and subsequently, the slurry 2 was dried. Thereafter, the slurry 2 was calcined at 450° C. for 30 minutes in air. In this manner, a first layer of the semiconductor electrode 2 was formed on the transparent electrode.
  • a second layer was formed on the first layer by using the slurry 1 and repeating application and calcination as described above.
  • a semiconductor electrode 2 (area of light-receiving surface: 1.0 cm 2 , total thickness of the first layer and the second layer: 10 ⁇ m (thickness of the first layer: 3 ⁇ m, thickness of the second layer: 7 ⁇ m)) was formed on the SnO 2 conductive film, and thus a photoelectrode 10 not containing any sensitizing dye, was produced.
  • an ethanol solution of the dye of the first embodiment of the present invention (concentration of sensitizing dye: 3 ⁇ 10 4 mol/L) was prepared as the sensitizing dye.
  • the photoelectrode 10 was immersed in this solution, and the photoelectrode was left immersed for 20 hours under the conditions of a temperature of 80° C. Thereby, the sensitizing dye was adsorbed to the interior of the semiconductor electrode in an amount of about 1.0 mmol/m 2 .
  • the semiconductor electrode after dye adsorption was immersed in an acetonitrile solution of 4-tert-butylpyridine for 15 minutes, and then was dried in a nitrogen gas stream maintained at 25° C.
  • the photoelectrode 10 was completed.
  • a counter electrode CE having the same shape and size as the photoelectrode was produced.
  • an isopropanol solution of chloroplatinic acid hexahydrate was added dropwise on a transparent conductive glass, dried in air, and then was calcination treated for 30 minutes at 450° C.
  • a platinum sintered counter electrode CE was obtained.
  • This counter electrode CE was provided in advance with a hole (diameter 1 mm) for the injection of an electrolyte E.
  • a spacer S (trade name: “Himilan”, an ethylene/methacrylic acid random copolymer ionomer film) manufactured by Mitsui-DuPont Polychemical, Ltd., which had a shape matching the size of the semiconductor electrode, was prepared, and as shown in FIG. 1 described in JP-A-2004-152613, the photoelectrode and the counter electrode were arranged to face each other, with the spacer interposed therebetween. The electrodes were respectively pasted by heat fusion. Thus, a casing of a cell (not filled with an electrolyte) was obtained.
  • a photoelectrochemical cell 2 was produced by the same procedure and the same conditions as in the case of the photoelectrochemical cell 1, except that the concentration of zinc iodide in the liquid electrolyte was changed to 50 mmol/L.

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CN104112787B (zh) * 2014-07-28 2016-04-13 武汉鑫神光电科技有限公司 一种硫化银/钙钛矿体异质结太阳能电池及其制备方法
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JP6555344B2 (ja) * 2015-05-08 2019-08-07 株式会社リコー 光電変換素子
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WO2018180112A1 (ja) * 2017-03-29 2018-10-04 保土谷化学工業株式会社 増感色素、光電変換用増感色素組成物およびそれを用いた光電変換素子ならびに色素増感太陽電池
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